[ { "id": "https://authors.library.caltech.edu/records/x034a-2ng26", "eprint_id": 107770, "eprint_status": "archive", "datestamp": "2023-08-20 01:35:47", "lastmod": "2024-01-15 21:22:22", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Volk\u00e1n-Kacs\u00f3-S\u00e1ndor", "name": { "family": "Volk\u00e1n-Kacs\u00f3", "given": "S\u00e1ndor" } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Single Molecule Studies of a Biological Motor F\u2081-ATPase: Interplay of Experiment, Analytic Theory and Computation", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 Springer Nature Switzerland AG 2021. \n\nFirst Online: 26 January 2021. \n\nThis work was supported by the Office of the Naval Research, the Army Research Office, and the James W. Glanville Foundation.", "abstract": "In this chapter we discuss the interaction between theory and single molecule experiments on a biological motor, F\u2081-ATPase. In particular, we consider an interplay between the experiment, analytical theory, and computer simulations. The complementarity of the millisecond and microsecond experiments is noted. For example, the limited experiments on the latter indicate that the ATP binding in one \u03b2 subunit precedes an ADP release in another \u03b2 subunit, whereas the millisecond experiments do not time-resolve the two steps.", "date": "2021-01-26", "date_type": "published", "publisher": "Springer International Publishing", "place_of_pub": "Cham", "pagerange": "927-933", "id_number": "CaltechAUTHORS:20210127-093006742", "isbn": "978-3-030-18777-4", "book_title": "Computational Materials, Chemistry, and Biochemistry: From Bold Initiatives to the Last Mile", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20210127-093006742", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "Army Research Office (ARO)" }, { "agency": "James W. Glanville Foundation" } ] }, "contributors": { "items": [ { "id": "Shankar-Sadasivan", "name": { "family": "Shankar", "given": "Sadasivan" } }, { "id": "Muller-Richard", "name": { "family": "Muller", "given": "Richard" } }, { "id": "Dunning-Thom-H", "name": { "family": "Dunning", "given": "Thom" } }, { "id": "Chen-Guan-Hua", "name": { "family": "Chen", "given": "Guan Hua" } } ] }, "doi": "10.1007/978-3-030-18778-1_38", "resource_type": "book_section", "pub_year": "2021", "author_list": "Volk\u00e1n-Kacs\u00f3, S\u00e1ndor and Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/ebkkc-gph83", "eprint_id": 97796, "eprint_status": "archive", "datestamp": "2023-08-19 10:54:13", "lastmod": "2023-10-18 16:45:03", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Volk\u00e1n-Kacs\u00f3-S", "name": { "family": "Volk\u00e1n-Kacs\u00f3", "given": "S\u00e1ndor" } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theory of Single Molecule Experiments of F_1-ATpase: Predictions, Tests and Comparison with Experiments", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 2018 World Scientific Publishing Co Pte Ltd.", "abstract": "There is now a substantial body of single molecule experiments on biomolecular motors, supplementing the extensive structural and ensemble data on these systems. Our current focus is on the motor, F_1-ATPase, a component of the enzyme ATP Synthase that uses proton gradients to synthesize ATP. Our interest is in seeing what information single molecule studies may provide on the relation between structural changes and the rates of various processes involved in the ATP binding, release, hydrolysis and synthesis. Our approach is to utilize a class of kinetic-thermodynamic relations used for chemical reactions and originally coming from the field of electron and other transfer reactions. To adapt those relations to biomolecular motors we incorporated into the kinetic-thermodynamic free energy expressions an elastic interaction between the rotor and stator subunits of the motor, and coupled the rotor to the chemical and physical processes. The theory is aimed at adding insights to the different of rates in terms of protein structure. On the more technical side another aim is to relate one type of single molecule experiment to another and to ensemble experiments. Theory-based predictions are made and compared with experiment. Some of our recent PNAS studies are summarized, together with more recent results.", "date": "2018-08", "date_type": "published", "publisher": "World Scientific", "place_of_pub": "Hackensack, NJ", "pagerange": "285-294", "id_number": "CaltechAUTHORS:20190812-145045521", "isbn": "9789813237162", "book_title": "Catalysis in Chemistry and Biology", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20190812-145045521", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "W\u00fcthrich-K", "name": { "family": "W\u00fcthrich", "given": "Kurt" } }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." } }, { "id": "Visart-de-Bocarm\u00e9-T", "name": { "family": "Visart de Bocarm\u00e9", "given": "Thierry" } }, { "id": "De-Wit-A", "name": { "family": "De Wit", "given": "Anne" } } ] }, "doi": "10.1142/9789813237179_0041", "resource_type": "book_section", "pub_year": "2018", "author_list": "Volk\u00e1n-Kacs\u00f3, S\u00e1ndor and Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/k0y5s-92t49", "eprint_id": 56147, "eprint_status": "archive", "datestamp": "2023-08-19 21:34:12", "lastmod": "2024-01-13 16:17:18", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Bisquert-J", "name": { "family": "Bisquert", "given": "Juan" } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Device Modeling of Dye-Sensitized Solar Cells", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2013 Springer-Verlag Berlin Heidelberg.\n\nPublished online: 28 September 2013.\n\nWe thank the following agencies for support of this research. Juan Bisquert's\nresearch is supported by Ministerio de Educacion y Ciencia under project HOPE CSD2007-00007, Generalitat Valenciana (ISIC/2012/008). Rudolph A. Marcus's research is supported by ARO, ONR and NSF agencies. Rudolph A. Marcus contributed in Sects. 14 and 15 of this chapter.", "abstract": "We review the concepts and methods of modeling of the dye-sensitized solar cell, starting from fundamental electron transfer theory, and using phenomenological transport-conservation equations. The models revised here are aimed at describing the components of the current\u2013voltage curve of the solar cell, based on small perturbation experimental methods, and to such an end, a range of phenomena occurring in the nanoparticulate electron transport materials, and at interfaces, are covered. Disorder plays a major role in the definition of kinetic parameters, and we introduce single particle as well as collective function definitions of diffusion coefficient and electron lifetime. Based on these fundamental considerations, applied tools of analysis of impedance spectroscopy are described, and we outline in detail the theory of recombination via surface states that is successful to describe the measured recombination resistance and lifetime.", "date": "2013-09-28", "date_type": "published", "publisher": "Springer", "place_of_pub": "Berlin", "pagerange": "325-395", "id_number": "CaltechAUTHORS:20150326-142337714", "isbn": "978-3-662-43873-2", "book_title": "Multiscale Modelling of Organic and Hybrid Photovoltaics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150326-142337714", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Ministerio de Educacion y Ciencia", "grant_number": "HOPE CSD2007-00007" }, { "agency": "Generalitat Valenciana", "grant_number": "ISIC/2012/008" }, { "agency": "Army Research Office (ARO)" }, { "agency": "Office of Naval Research (ONR)" }, { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Beljonne-D", "name": { "family": "Beljonne", "given": "David" } }, { "id": "Cornil-J", "name": { "family": "Cornil", "given": "Jerome" } } ] }, "doi": "10.1007/128_2013_471", "resource_type": "book_section", "pub_year": "2013", "author_list": "Bisquert, Juan and Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/c9fvz-zsr80", "eprint_id": 45686, "eprint_status": "archive", "datestamp": "2023-08-19 09:16:01", "lastmod": "2024-01-13 16:05:05", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Michel-Beyerle-M-E", "name": { "family": "Michel-Beyerle", "given": "Maria-Elisabeth" } } ] }, "title": "Foreword", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 Royal Society of Chemistry 2012.\n\n
Published - 9781849733038-fp005.pdf
", "abstract": "It has been increasingly recognized that one of the major problems facing\nour generation and later ones is the reliance on fossil fuels, their effect on\nclimate, their gradual exhaustion, and the great need for alternative energy\nsources. Since the most conspicuous and abundant source of energy is the\nsun, solar energy conversion has become the magical concept to conjure\nthe development of organic and inorganic photovoltaics and, even better, the\ndirect production of chemical energy carriers.", "date": "2012", "date_type": "published", "publisher": "Royal Society of Chemistry", "place_of_pub": "Cambridge, UK", "pagerange": "5-6", "id_number": "CaltechAUTHORS:20140512-120711093", "isbn": "978-1-84973-034-1", "book_title": "Molecular Solar Fuels", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20140512-120711093", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "Wydrzynski-T-J", "name": { "family": "Wydrzynski", "given": "Thomas J." } }, { "id": "Hillier-W", "name": { "family": "Hillier", "given": "Warwick" } } ] }, "doi": "10.1039/9781849733038-FP005", "primary_object": { "basename": "9781849733038-fp005.pdf", "url": "https://authors.library.caltech.edu/records/c9fvz-zsr80/files/9781849733038-fp005.pdf" }, "resource_type": "book_section", "pub_year": "2012", "author_list": "Marcus, Rudolph A. and Michel-Beyerle, Maria-Elisabeth" }, { "id": "https://authors.library.caltech.edu/records/bk90e-rke38", "eprint_id": 55791, "eprint_status": "archive", "datestamp": "2023-08-20 01:16:25", "lastmod": "2023-10-20 23:13:17", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Beyond the Historical Perspective on Hydrogen and Electron Transfers", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 2009 Royal Society of Chemistry.\n\nMany authors have made major contributions to the electron-transfer and H-transfer fields, as seen in the copious citations in the present volume. I am indebted to Judith Klinman, Amnon Kohen, Sharon Hammes-Schiffer and Maria-Elisabeth Michel-Beyerle for their helpful comments. The research described in this preface was supported by the National Science Foundation and the Office of Naval Research. Recent reviews and other articles are cited in the author's J. Phys. Chem. B, 2007, 111, 6643 and J. Chem. Phys., 2006, 25, Art. No. 194504, which also elaborate on several of the topics mentioned here.\n\nPublished - 9781847559975-fp005.pdf
", "abstract": "A brief overview of proton and electron transfer history is given, and various\nfeatures influencing enzymatic catalysis are discussed. Examples of generic\nbehavior are considered, together with questions that can be addressed for both\nexperimental and computational results. Examples of high and low pre-exponential\nfactors A of the intrinsic rate constant k_H ranging from ~10^(17) s^(-1) to ~10^4 s^(-1) and normal (~10^(13)) are noted with significant error bars and\ndiscussed.", "date": "2009-03-27", "date_type": "published", "publisher": "Royal Society of Chemistry", "place_of_pub": "Cambridge, UK", "pagerange": "v-xiv", "id_number": "CaltechAUTHORS:20150316-125057976", "isbn": "978-0-85404-122-0", "book_title": "Quantum Tunnelling in Enzyme-Catalysed Reactions", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150316-125057976", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Allemann-R-K", "name": { "family": "Allemann", "given": "Rudolf K." } }, { "id": "Scrutton-N-S", "name": { "family": "Scrutton", "given": "Nigel S." } } ] }, "doi": "10.1039/9781847559975-FP005", "primary_object": { "basename": "9781847559975-fp005.pdf", "url": "https://authors.library.caltech.edu/records/bk90e-rke38/files/9781847559975-fp005.pdf" }, "resource_type": "book_section", "pub_year": "2009", "author_list": "Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/ynckj-7x643", "eprint_id": 55850, "eprint_status": "archive", "datestamp": "2023-08-19 22:36:43", "lastmod": "2024-01-13 16:16:57", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Mass-Independent Oxygen Isotope Fractionation in Selected Systems. Mechanistic Considerations", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 2008 Elsevier Inc.\n\nAvailable online 26 April 2008.\n\nIt is a pleasure to acknowledge the support of this research by the National Science Foundation and the very helpful comments of anonymous reviewers.", "abstract": "Studies of the mass-independent effect on oxygen isotope fractionation (MIF) are summarized, focusing on the MIF in ozone formation in the laboratory, a similar effect being found in the atmosphere. (As used here the MIF for O isotopomers means that the usual three-isotope plot has a slope of about unity instead of the conventional 0.52.) The marked difference of results obtained with systems when there is extensive isotopic exchange (\"scrambled\") and experimental conditions where isotopic exchange is minimized (\"unscrambled\") is also discussed. Ratios of rate constants can be measured only in the latter and show large isotope effects. These large isotope effects were shown to cancel exactly when there is extensive isotopic exchange, and one then obtains instead an MIF for ozone. We also consider a possible role of the chaperon versus energy transfer mechanisms for ozone formation in influencing the temperature dependence of the MIF. MIF in other systems are noted. Separately we consider the CO+OH\u2192CO_2 reaction, an isotopically anomalous reaction. It has sometimes been called \"mass-independent\" but has no O atom symmetry for the HOCO\u2217 intermediate and so no MIF in the above sense (ca. unit slope) would be expected on theoretical grounds.", "date": "2008-05", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "Boston, MA", "pagerange": "5-19", "id_number": "CaltechAUTHORS:20150317-103239277", "isbn": "9780123743350", "book_title": "Applications of Theoretical Methods to Atmospheric Science", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150317-103239277", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Sabin-J-R", "name": { "family": "Sabin", "given": "John R." } }, { "id": "Br\u00e4ndas-E", "name": { "family": "Br\u00e4ndas", "given": "Erkki" } } ] }, "doi": "10.1016/S0065-3276(07)00202-X", "resource_type": "book_section", "pub_year": "2008", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/gk98r-0tj20", "eprint_id": 55892, "eprint_status": "archive", "datestamp": "2023-08-19 21:51:36", "lastmod": "2024-01-13 16:16:59", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Young-E-D", "name": { "family": "Young", "given": "Edward D." } }, { "id": "Kuramoto-K", "name": { "family": "Kuramoto", "given": "Kyoshi" } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Yurimoto-H", "name": { "family": "Yurimoto", "given": "Hisayoshi" } }, { "id": "Jacobsen-S-B", "name": { "family": "Jacobsen", "given": "Stein B." } } ] }, "title": "Mass-independent Oxygen Isotope Variation in the Solar Nebula", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 The Mineralogical Society Of America.", "abstract": "In this chapter we compare and contrast chemical and photochemical pathways for mass-independent fractionation (MIF) of oxygen isotopes in the solar nebula. We begin by assessing the galactic evolution model for oxygen isotope variation in the Solar System in order to compare the predictions of a leading nucleosynthetic model with those of the chemical models. There are two fundamentally different classes of possible chemical mechanisms for mass-independent oxygen isotope fractionation in the early Solar System. One is symmetry-induced intramolecular vibrational disequilibrium of vibrationally excited reactant oxygen-bearing molecules. The other is isotope selective photodissociation of CO coupled with self-shielding and formation of H_2O. Symmetry-induced fractionation is an experimentally verified process with solid theoretical foundations. It is observed to occur in Earth's atmosphere. It could have resulted in preservation of oxygen MIF effects only if mediated by dust grain surfaces. CO self-shielding is an attractive hypothesis for the origin of mass-independent oxygen isotope fractionation in the early Solar System because it appeals to a process that apparently occurs in the interstellar medium, but it lacks experimental verification. Three astrophysical settings for CO self-shielding are proposed as sites for generating \u0394^(17)O variability in the early Solar System. One is the inner annulus of the protostellar disk at relatively high temperature. Another is the surface of the disk high above the midplane where light from the central star grazes the gas and dust of the disk, resulting in a zone of active CO predissociation and self-shielding. Interstellar light illuminating the disk at high incident angles causes a similar horizon of CO photodestruction. Variations in ^(16)O could also have been inherited from self-shielding by CO in the molecular cloud that gave rise to the protosun. The overall consequence of CO self-shielding is conversion of CO gas to ^(16)O-poor H_2O. A key difference between galactic evolution, chemically-induced MIF effects, and CO self-shielding is the predicted relative oxygen isotopic compositions of primeval dust and the Sun. Therefore, the oxygen isotopic composition of the Sun will be a crucial arbiter that may permit us to narrow the list of possible origins for oxygen MIF in the early Solar System.", "date": "2008", "date_type": "published", "publisher": "Mineralogical Society of America", "place_of_pub": "Chantilly, VA", "pagerange": "187-218", "id_number": "CaltechAUTHORS:20150318-112508668", "isbn": "978-0-939950-80-5", "book_title": "Oxigen in the Solar System", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150318-112508668", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "MacPherson-G-J", "name": { "family": "MacPherson", "given": "Glenn J." } }, { "id": "Mittlefehldt-D-W", "name": { "family": "Mittlefehldt", "given": "David W." } }, { "id": "Jones-J-H", "name": { "family": "Jones", "given": "John H." } }, { "id": "Simon-S-B", "name": { "family": "Simon", "given": "Steven B." } } ] }, "doi": "10.2138/rmg.2008.68.9", "resource_type": "book_section", "pub_year": "2008", "author_list": "Young, Edward D.; Kuramoto, Kyoshi; et el." }, { "id": "https://authors.library.caltech.edu/records/qwxqe-taj68", "eprint_id": 58583, "eprint_status": "archive", "datestamp": "2023-08-19 04:18:18", "lastmod": "2023-10-23 19:30:02", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Interaction of Theory and Experiment in Reaction Kinetics", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1999 Elsevier Science B.V. \n\nIt is a real pleasure to dedicate this article to John Albery and to recognize his influential and joyous contributions to this interaction of experimentalists and theorists. It is a pleasure too to acknowledge the many contributions of my coworkers whose work is described in this chapter. This research was supported by the National Science Foundation and by the Office of Naval Research and I am very pleased to acknowledge that support.", "abstract": "The interaction of experiment and theory clearly delights John Alberya colleague and friend to whom this chapter is dedicated. That interaction is the principal theme of this contribution. The examples given below are taken from the experiences of my research group in a number of fields in,\nor related to, reaction kinetics:\n(1) high-resolution spectroscopic studies and intramolecular vibrational energy migration;\n(2) long-range electron transfer (ET) in proteins;\n(3) ET in a broad range of systems;\n(4) ion, atom and group transfers;\n(5) photosynthetic reaction center ET;\n(6) solvent dynamics and the chemists' delayed use of Kramers' theory;\n(7) unimolecular reaction rates and products' distribution of rotational-vibrational quantum states;\n(8) unimolecular reaction rates in clusters;\n(9) vibrational adiabaticity and reaction coordinates;\n(10) graph theory and additivity in delocalized (aromatic) molecules.", "date": "1999-05", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "New York, NY", "pagerange": "1-33", "id_number": "CaltechAUTHORS:20150624-111043594", "isbn": "978-0-444-50164-6", "book_title": "Applications of Kinetic Modelling", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150624-111043594", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Compton-R-G", "name": { "family": "Compton", "given": "R. G." } }, { "id": "Hancock-G", "name": { "family": "Hancock", "given": "G." } } ] }, "doi": "10.1016/S0069-8040(99)80006-5", "resource_type": "book_section", "pub_year": "1999", "author_list": "Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/b3c34-mt191", "eprint_id": 58164, "eprint_status": "archive", "datestamp": "2023-08-22 13:24:40", "lastmod": "2024-01-13 16:21:22", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electron Transfer Past and Future", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "electron transfer; polymers; photoexcitation; reorganization energy; photosynthesis", "note": "\u00a9 1999 John Wiley & Sons, Inc.\n\nIt is a pleasure for me to acknowledge the support of my electron transfer\nresearch during these many years by the National Science Foundation and\nby the Office of Naval Research.", "abstract": "Electron transfers in the post-World War II era began in the small arcane\nfield of isotopic self-exchange reactions, such as Fe^(3+) * + Fe^(2+) \u2192 Fe^(2+) * + Fe^(3+),\nin solution. There was an abundance of radioactive isotopes (denoted here by\nan asterisk), and chemists were using isotopic tracers after the war to determine\nthe mechanisms of various chemical reactions. Their use in electron\ntransfer was very fortunate, since it removed from consideration one of the\ndominant factors controlling chemical reaction rates, \u0394G^0, the standard free\nenergy of reaction or, as it is commonly called, the driving force of the reaction.\nThis \u0394G^0 vanishes for self-exchange reactions.", "date": "1999", "date_type": "published", "publisher": "Wiley", "place_of_pub": "New York, NY", "pagerange": "1-6", "id_number": "CaltechAUTHORS:20150610-125823518", "isbn": "9780471252924", "book_title": "Electron Transfer-From Isolated Molecules to Biomolecules", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150610-125823518", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Prigogine-I", "name": { "family": "Prigogine", "given": "I." } }, { "id": "Rice-S-A", "name": { "family": "Rice", "given": "S. A." } } ] }, "doi": "10.1002/9780470141656.ch1", "resource_type": "book_section", "pub_year": "1999", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/cr1t3-33051", "eprint_id": 56804, "eprint_status": "archive", "datestamp": "2023-08-19 00:47:41", "lastmod": "2024-01-13 16:17:44", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Solvent Dynamics and RRKM Theory of Clusters", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1997 John Wiley & Sons, Inc.\n\nIt is a pleasure to acknowledge the support of this research by the National Science\nFoundation and the Office of Naval Research.", "abstract": "In this chapter we consider the problem of reaction rates in clusters (microcanonical)\nmodified by solvent dynamics. The field is a relatively new one,\nboth experimentally and theoretically, and stems from recent work on well-defined\nclusters. We first review some theories and results for the\nsolvent dynamics of reactions in constant-temperature condensed-phase systems\nand then describe two papers from our recent work on the adaptation to\nmicrocanonical systems. In the process we comment on a number of questions\nin the constant-temperature studies and consider the relation of those\nstudies to corresponding future studies of clusters.", "date": "1997", "date_type": "published", "publisher": "Wiley", "place_of_pub": "New York, NY", "pagerange": "391-408", "id_number": "CaltechAUTHORS:20150421-093424183", "isbn": "9780471180487", "book_title": "Chemical reactions and their control on the femtosecond time scale", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150421-093424183", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Gaspard-P", "name": { "family": "Gaspard", "given": "Pierre" } }, { "id": "Burghardt-I", "name": { "family": "Burghardt", "given": "Irene" } }, { "id": "Prigogine-I", "name": { "family": "Prigogine", "given": "I." } }, { "id": "Rice-S-A", "name": { "family": "Rice", "given": "Stuart A." } } ] }, "resource_type": "book_section", "pub_year": "1997", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/j5572-8qw16", "eprint_id": 58314, "eprint_status": "archive", "datestamp": "2023-08-19 00:47:49", "lastmod": "2023-10-23 19:14:50", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Transition State Theory and Experiments in Chemical Reactions", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1997 Imperial College Press.\n\nIt is a real pleasure to acknowledge the support of this research by the National Science Foundation and the Office of Naval Research. It is also a pleasure to acknowledge many stimulating conversations with my colleague, Ahmed Zewail. The references given below are intended to be illustrative rather than comprehensive.", "abstract": "The transition state theory of chemical reactions has proven to be a formidable tool for analyzing chemical reaction rates of a wide variety of reactions. In the present article some of its developments, extensions, and applications are described. \nTransition state theory was developed in its current form by Eyring and Evans and Polanyi in 1935, only about a half a dozen years after the quantum mechanical description of potential energy surfaces by London for chemical reactions. The advances in the understanding of the dynamics in the 1930s were rapid, particularly by Hirschfelder, Wigner, and O.K. Rice, among others. A number of the problems, concepts, and themes that are currently discussed were considered at that time, and even some classical trajectory calculations were made then by Hirschfelder. \nThere was another thread in chemical reaction rate theory, unimolecular reaction rate theory, which developed earlier in the 1920s, the initial work being that of Hinshelwood, followed by the more detailed theory of Rice and Ramsperger and of Kassel, which became well known as the RRK theory. That tl1eory was applied to and stimulated extensive experiments on the unimolecular decomposition of organic molecules during the 1920s and early 1930s. However, such experiments revealed that those reactions had complex mechanisms: They were found to proceed via a series of elementary steps involving free radicals as intermediates, rather than occurring in a single step. A new field of study, reaction rates and mechanisms, and later the direct spectral observation, of gas phase free radicals was born. The use of unimolecular theory went into decline-there were practically no systems to which it could be applied and which could stimulate its further growth. During 1939-45 there was a general lull, however, in all these activities because of the Second World War. \nInterest in unimolecular theory resumed in the late 1940s with N. B. Slater's sophisticated and exciting extension of earlier ideas of Polanyi and Wigner and Peltzer. His work was based on treating the decomposing or isomerizing molecule as a collection of harmonic oscillators. The neglect of the effects of anharmonic coupling, and the results of various incisive experiments, led later to its abandonment as a method for treating the emerging experimental data on these reactions. Nevertheless, it introduced new and refreshing ideas into the field. \nIn 1949, as a postdoctoral with O.K. Rice, I blended ideas drawn from transition state and RRK theories and formulated a molecular structure-based statistical theory for these reactions. The time was ripe for this development. New molecular ideas, such as potential energy surfaces, had developed only after RRK theory had been formulated, and post-war research was beginning to flourish. My own interest stemmed from the experimental work I had done on the unimolecular decomposition of the CH_3OCH_2 free radical and on the recombination of methyl radicals in the laboratory of E.W.R. Steacie in Canada. \nThis unimolecular theory, known since the 1960s as RRKM theory, is in current use today. To treat reactions for which the reverse reaction of bimolecular association has no energy barrier, the defining the position of the transition state (TS) becomes a problem. A variational form of the theory was subsequently developed to determine the TS, and has been extensively applied. \nIn the present paper I comment on a number of types of reactions investigated with transition state theory and on some of the features which arise when specific aspects of the reaction or of the potential energy surfaces are introduced. They include electron transfers, energy dependence of unimolecular reaction rates in the gas phase, unimolecular reactions in clusters, including solvent dynamics, global contour plots for reactions, S_N2 reactions, and extensions of transition state theory which include, in addition to reaction rates, the distribution of quantum states of the reaction products of unimolecular dissociations. In the latter we again consider dissociations in which there is no energy barrier for the reverse reaction, the recombination of the fragments. \n\nA striking feature in this history is that some sixty years after the development of transition state theory it continues to be a useful tool for chemists, to which additional concepts can be added. The field of chemical reaction rates itself has been stimulated by the new types of data which are becoming available with ultrafast techniques, as well as by the earlier classical techniques applied to interesting systems.", "date": "1997", "date_type": "published", "publisher": "Imperial College Press", "place_of_pub": "London", "pagerange": "54-79", "id_number": "CaltechAUTHORS:20150617-094941310", "isbn": "9781860940392", "book_title": "Femtochemistry and femtobiology : ultrafast reaction dynamics at atomic-scale resolution", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150617-094941310", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" }, { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Sundstr\u00f6m-V", "name": { "family": "Sundstr\u00f6m", "given": "Villy" } } ] }, "resource_type": "book_section", "pub_year": "1997", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/q0y1a-5b857", "eprint_id": 58585, "eprint_status": "archive", "datestamp": "2023-08-20 07:08:21", "lastmod": "2023-10-23 19:30:09", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electron transfer experiments since the late 1940s", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1996 Bios Scientific Publishers Ltd. \n\nPublication Date: June 14, 1996. \n \nMy acknowledgments are to my many fellow researchers in the electron transfer field, notably Norman Sutin, with whom I have discussed so many of these matters for the past 30 or more years. I also thank my students and postdoctorals, whose presence was a constant source of stimulation to me, both in the electron transfer field and in the other fields of research which we have explored. In its earliest stage and for much of this period, this research was supported by the Office of Naval Research and also later by the National\nScience Foundation. The support of both agencies continues to this day and I am very pleased to acknowledge its value and timeliness here. In my Nobel lecture, I concluded on a personal note with a slide of my great-uncle, Henrik\nSteen (n\u00e9 Markus), who came to Sweden in 1892. He received his doctorate in theology from the University of Uppsala in 1915, and was an educator and a prolific writer of pedagogic books. As I noted in the biographical sketch in Les Prix Nobel, he was one of my childhood idols. Coming here, visiting with my Swedish relatives - some 30 or so of his descendants - has been an especially heartwarming experience for me and for my family. In a sense I feel that I owed him a debt, and that it is most fitting to acknowledge that debt here.", "abstract": "Since the late 1940s, the field of electron transfer processes has grown enormously, both in chemistry and biology. The development of the field, experimentally and theoretically, as well as its relationship to the study of other kinds of chemical reactions, represents to us an intriguing history, one in which many threads have been brought together. In this chapter, some history, recent\ntrends and my own involvement in this research are described.", "date": "1996-01-01", "date_type": "published", "publisher": "Bios Scientific Publishers", "place_of_pub": "London", "pagerange": "249-272", "id_number": "CaltechAUTHORS:20150624-114923116", "isbn": "9781859960400", "book_title": "Protein electron transfer", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150624-114923116", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Bendall-D-S", "name": { "family": "Bendall", "given": "D. S." } } ] }, "resource_type": "book_section", "pub_year": "1996", "author_list": "Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/p37ep-31d11", "eprint_id": 59905, "eprint_status": "archive", "datestamp": "2023-08-23 16:52:17", "lastmod": "2023-10-23 22:49:08", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electron Transfer Reactions in Chemistry: Theory and Experiment", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1992 Imprimerie Royale.\n\nMy acknowledgments are to my many fellow researchers in the electron\ntransfer field, notably Norman Sutin, with whom I have discussed so many\nof these matters for the past thirty or more years. I also thank my students\nand post-doctorals, whose presence was a constant source of stimulation to\nme, both in the electron transfer field and in the other fields of research which we have explored. In its earliest stage and for much of this period this\nresearch was supported by the Office of Naval Research and also later by\nthe National Science Foundation. The support of both agencies continues\nto this day and I am very pleased to acknowledge its value and timeliness\nhere.", "abstract": "Since the late 1940s, the field of electron transfer processes has grown\nenormously, both in chemistry and biology. The development of the field,\nexperimentally and theoretically, as well as its relation to the study of other\nkinds of chemical reactions, represents to us an intriguing history, one in\nwhich many threads have been brought together. In this lecture, some\nhistory, recent trends, and my own involvement in this research are described.", "date": "1992-12-08", "date_type": "published", "publisher": "Imprimerie Royale", "id_number": "CaltechAUTHORS:20150826-103310579", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150826-103310579", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "NSF" } ] }, "resource_type": "book_section", "pub_year": "1992", "author_list": "Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/9bbj1-ew160", "eprint_id": 58151, "eprint_status": "archive", "datestamp": "2023-08-20 00:48:52", "lastmod": "2024-01-13 16:21:20", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Siddarth-P", "name": { "family": "Siddarth", "given": "Prabha" } } ] }, "title": "Theory of Electron Transfer Reactions and Comparison with Experiments", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1992 Kluwer Academic Publishers.\n\nIt is a pleasure to acknowledge the support of this work by the Office of Naval\nResearch and by the National Science Foundation. A portion of these lectures\nwas written while one of us (R.A.M.) was the Baker Lecturer at Cornell\nUniversity. He is very pleased to acknowledge the hospitality and discussions\nof his colleagues there.", "abstract": "In these lectures, reaction rate theory and the theory of electron\ntransfer (ET) reactions are outlined. The topics discussed include the relation\nof the potential energy surfaces to free energy curves for ET reactions, classical\nET theory for reactions in solution and at interfaces, quantum corrections, the\ninverted effect, relation to charge transfer spectra, the cross-relation, adiabatic\nand nonadiabatic ET reactions, electronic matrix elements, relation to other\ntransfer reactions, predictions of and comparison with experiments, and\nmiscellaneous questions.", "date": "1992", "date_type": "published", "publisher": "Kluwer", "place_of_pub": "Dordrecht", "pagerange": "49-88", "id_number": "CaltechAUTHORS:20150610-104009327", "isbn": "9780792319368", "book_title": "Photoprocesses in transition metal complexes, biosystems, and other molecules: experiment and theory", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150610-104009327", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Kochanski-E", "name": { "family": "Kochanski", "given": "Elise" } } ] }, "resource_type": "book_section", "pub_year": "1992", "author_list": "Marcus, R. A. and Siddarth, Prabha" }, { "id": "https://authors.library.caltech.edu/records/crk4s-0h885", "eprint_id": 85642, "eprint_status": "archive", "datestamp": "2023-08-20 00:02:52", "lastmod": "2024-01-14 19:34:55", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Epilogue", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1991 American Chemical Society. \n\nReceived May 17, 1990. Published in print 5 May 1991.", "abstract": "THE FIELD OF ELECTRON-TRANSFER REACTIONS has expanded dramatically since the early days in the late 1940s and the 1950s when the rates of many such reactions (isotopic-exchange reactions) were studied by using isotopic labeling techniques. The chapters in this volume demonstrate some of the more recent developments. They speak eloquently for themselves, and my summary will be relatively brief.", "date": "1991-05-05", "date_type": "published", "publisher": "American Chemical Society", "id_number": "CaltechAUTHORS:20180405-131938383", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20180405-131938383", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "doi": "10.1021/ba-1991-0228.ch018", "resource_type": "book_section", "pub_year": "1991", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/k15c8-1a235", "eprint_id": 58312, "eprint_status": "archive", "datestamp": "2023-08-19 22:14:07", "lastmod": "2024-01-13 16:22:30", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "Rudolph A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theory and Experiment in Photosynthetic Electron Transfer", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1990 Kluwer Academic Publishers.\n\nIt is a pleasure to acknowledge the support of this research by the Office of Naval Research and the National Science Foundation.", "abstract": "The recent determination of the crystallographic structure of a bacterial\nphotosynthetic reaction center has provided an important framework for\ntreating electron transfers in these systems. As in electron transfers in\nsimpler systems, a knowledge of both the structure and the thermodynamics is\nneeded for understanding the experimental results on reaction rates at the\nfundamental level. In this lecture we first describe the theory of simple\nelectron transfer reaction rates, and then consider how the resulting\ninteraction between theory and experiment may assist us in treating electron\ntransfers in the photosynthetic reaction center.\nIn the final portion of this talk we summarize a view of the current state\nof knowledge in this electron transfer complex, and some of the questions\nwhich remain. We include in our discussion the very recent and dramatic\nresults of Zinth and coworkers on the role of the bacteriochlorophyll monomer\nat room temperature (2), presented also at this Congress. Ultimately, all of the\nevidence for the mechanism should fit. In bacterial photosynthesis we have\nnot yet reached that state, but several recent developments have perhaps\nbegun to simplify the picture, examined in this lecture.", "date": "1990", "date_type": "published", "publisher": "Kluwer Academic Publishers", "place_of_pub": "Dordrecht", "pagerange": "1-10", "id_number": "CaltechAUTHORS:20150617-093412278", "isbn": "9780792305873", "book_title": "Current research in photosynthesis: Proceedings of the VIIIth International Conference on Photosynthesis Stockholm, Sweden, August 6-11, 1989", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150617-093412278", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" }, { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Baltscheffsky-M", "name": { "family": "Baltscheffsky", "given": "Margareta" } } ] }, "doi": "10.1007/978-94-009-0511-5_1", "resource_type": "book_section", "pub_year": "1990", "author_list": "Marcus, Rudolph A." }, { "id": "https://authors.library.caltech.edu/records/hra67-6bs02", "eprint_id": 58673, "eprint_status": "archive", "datestamp": "2023-08-19 20:06:21", "lastmod": "2024-01-13 16:23:14", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Early Steps in Bacterial Photosynthesis. Comparison of Three Mechanisms", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1988 Springer Science+Business Media New York.\n\nIt is a pleasure to acknowledge the support of this research by the Office of Naval Research. This article is Contribution No. 7707 from the Department of Chemistry.", "abstract": "Mechanisms for the early electron transfer steps in the bacterial\nphotosynthetic reaction center are discussed. An internal consistency test is\ndescribed which places a real constraint on the unknown parameters. A\nresulting possible paradox is described, together with proposed electric field\nmeasurements and an alternate mechanism.", "date": "1988", "date_type": "published", "publisher": "Springer", "place_of_pub": "New York. NY", "pagerange": "389-398", "id_number": "CaltechAUTHORS:20150629-123934011", "isbn": "978-1-4899-0817-9", "book_title": "The Photosynthetic Bacterial Reaction Center: Structure and Dynamics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150629-123934011", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" } ] }, "other_numbering_system": { "items": [ { "id": "7707", "name": "Caltech Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Breton-J", "name": { "family": "Breton", "given": "Jacques" } }, { "id": "Vermeglio-A", "name": { "family": "Vermeglio", "given": "Andr\u00e9" } } ] }, "doi": "10.1007/978-1-4899-0815-5_39", "resource_type": "book_section", "pub_year": "1988", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/kb26m-5bx25", "eprint_id": 58682, "eprint_status": "archive", "datestamp": "2023-08-22 05:35:45", "lastmod": "2024-01-13 16:23:16", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Wardlaw-D-M", "name": { "family": "Wardlaw", "given": "David M." } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "On the Statistical Theory of Unimolecular Processes", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "RRKM theory; angular momentum conservation; CH_3 recombination; NCNO dissociation; H_2CO dissociation", "note": "\u00a9 1988 by John Wiley & Sons, Inc. Published Online: 14 Mar 2007. \n\nNSERC of Canada University Research Fellow. It is a pleasure to acknowledge the support of this research by the Natural Sciences and Engineering Research Council of Canada (D.M.W.) and by the National Science Foundation (R.A.M.).", "abstract": "In recent years there has been an increasing use of laser spectroscopic and other techniques to investigate unimolecular dissociations of molecules, both to initiate a dissociation and to measure the formation of the individual\nquantum states of the immediate reaction products. This chapter is concerned with a description of statistical theories used to calculate the rates of such dissociations, for example, of a molecule AB, AB \u2192 A + B, and to calculate the distribution of the quantum states of the fragments A and B.", "date": "1988", "date_type": "published", "publisher": "Wiley", "place_of_pub": "Hoboken, NJ", "pagerange": "231-263", "id_number": "CaltechAUTHORS:20150629-145635893", "isbn": "978-0-470-14179-3", "book_title": "Evolution of Size Effects in Chemical Dynamics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150629-145635893", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Natural Sciences and Engineering Research Council of Canada (NSERC)" }, { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "7473", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Prigogine-I", "name": { "family": "Prigogine", "given": "I." } }, { "id": "Rice-S-A", "name": { "family": "Rice", "given": "Stuart A." } } ] }, "doi": "10.1002/9780470141199.ch7", "resource_type": "book_section", "pub_year": "1988", "author_list": "Wardlaw, David M. and Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/bd5q8-wa516", "eprint_id": 58696, "eprint_status": "archive", "datestamp": "2023-08-19 19:08:45", "lastmod": "2023-10-23 19:37:37", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Solvent Dynamical and Symmetrized Potential Aspects of Electron Transfer Rates", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1987 by D. Reidel Publishing Company. \n\nThe support of this research by the National Science Foundation is gratefully acknowledged. Carl and Ingrid, we salute you, and extend our very best wishes for the future.", "abstract": "Recent experiments on very fast electron transfers have provided evidence for slow solvent dynamics under such conditions. The role of the vibrational motion of the reactants is included in the present treatment. The overall decay can be single- or multi-exponential. A simple approximate expression is given for a characteristic reaction time. The \"symmetrization\" approximation in the cross-relation is also discussed.", "date": "1987", "date_type": "published", "publisher": "Springer", "place_of_pub": "Dordrecht", "pagerange": "229-236", "id_number": "CaltechAUTHORS:20150630-094059392", "isbn": "978-94-010-8182-5", "book_title": "Understanding Molecular Properties", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150630-094059392", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "7396", "name": "Caltech Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Avery-J", "name": { "family": "Avery", "given": "John" } }, { "id": "Dahl-P-J", "name": { "family": "Dahl", "given": "Peder Jens" } }, { "id": "Hansen-A-E", "name": { "family": "Hansen", "given": "Aage E." } } ] }, "doi": "10.1007/978-94-009-3781-9_13", "resource_type": "book_section", "pub_year": "1987", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/rsb9g-b8m65", "eprint_id": 58695, "eprint_status": "archive", "datestamp": "2023-08-19 19:08:38", "lastmod": "2024-01-13 16:23:18", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Some Recent Developments in Electron Transfer: Charge Separation, Long Distances, Solvent Dynamics, and Free Energy Aspects", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1987 by D. Reidel Publishing Company. \n\nIt is a pleasure to acknowledge the support of this research by the Office of Naval Research and the National Science Foundations. The present article is No. 7569 from the Department of Chemistry.", "abstract": "Several topics in electron transfers are discussed, including the charge separation in a bacterial photosynthetic reaction center, long range electron transfers, solvent dynamical effects in electron transfer, and free energy aspects of these reactions.", "date": "1987", "date_type": "published", "publisher": "Springer", "place_of_pub": "Dordrecht", "pagerange": "45-52", "id_number": "CaltechAUTHORS:20150630-092517105", "isbn": "978-94-010-8265-5", "book_title": "Supramolecular Photochemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150630-092517105", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research" }, { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "7569", "name": "Caltech Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Balzani-V", "name": { "family": "Balzani", "given": "Vincenzo" } } ] }, "doi": "10.1007/978-94-009-3979-0_3", "resource_type": "book_section", "pub_year": "1987", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/ddr07-a1374", "eprint_id": 58725, "eprint_status": "archive", "datestamp": "2023-08-19 17:27:22", "lastmod": "2024-01-13 16:23:20", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Sutin-N", "name": { "family": "Sutin", "given": "N." } } ] }, "title": "Application of Electron-Transfer Theory to Several Systems of Biological Interest", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1985 Springer Berlin Heidelberg.\n\nResearch at Brookhaven National Laboratory (N.S.) was\nperformed under contract DE-AC02-76CH00016 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Office of Basic Energy Sciences, while that at Caltech (R.A.M.) was supported by the National Science Foundation and the Office of Naval Research.", "abstract": "Electron-transfer reaction rates are compared with theoretically calculated values for several reactions in the bacterial photosynthetic reaction center. A second aspect of the theory, the cross-relation, is illustrated using protein-protein electron-transfers.", "date": "1985", "date_type": "published", "publisher": "Springer", "place_of_pub": "Berlin", "pagerange": "226-233", "id_number": "CaltechAUTHORS:20150701-080055856", "isbn": "978-3-642-82690-0", "book_title": "Antennas and Reaction Centers of Photosynthetic Bacteria: Structure, Interactions and Dynamics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-080055856", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-AC02-76CH00016" }, { "agency": "NSF" }, { "agency": "Office of Naval Research" } ] }, "other_numbering_system": { "items": [ { "id": "7248", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Michel-Beyerle-M-E", "name": { "family": "Michel-Beyerle", "given": "M. E." } } ] }, "doi": "10.1007/978-3-642-82688-7_32", "resource_type": "book_section", "pub_year": "1985", "author_list": "Marcus, R. A. and Sutin, N." }, { "id": "https://authors.library.caltech.edu/records/ccsh8-h8d95", "eprint_id": 58726, "eprint_status": "archive", "datestamp": "2023-08-19 17:27:29", "lastmod": "2024-01-13 16:23:22", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Aspects of Intramolecular Dynamics in Chemistry", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1985 Springer International Publishing.\n\nIt is a pleasure to acknowledge the support of this research by a grant from the National Science Foundation. Contribution No. 6894 from the California Institute of Technology.", "abstract": "The role of chaotic and quasiperiodic behavior of isolated molecules is discussed. The quantum analog of classical quasi- periodic states appears to be relatively well understood. A possible quantum analog of classical chaotic behavior is described, using overlapping quantum mechanical Fermi resonances as a way of generating irregularities. The relation of these Fermi resonances to avoided crossings in eigenvalue plots and to various treatments of intramolecular dynamics in the chemical literature is outlined.", "date": "1985", "date_type": "published", "publisher": "Springer", "place_of_pub": "New York, NY", "pagerange": "293-298", "id_number": "CaltechAUTHORS:20150701-082708661", "isbn": "978-1-4612-9485-6", "book_title": "Chaotic Behavior in Quantum Systems", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-082708661", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "6894", "name": "Caltech Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Casati-G", "name": { "family": "Casati", "given": "G." } } ] }, "doi": "10.1007/978-1-4613-2443-0_19", "resource_type": "book_section", "pub_year": "1985", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/mr05x-kz788", "eprint_id": 58727, "eprint_status": "archive", "datestamp": "2023-08-19 16:31:51", "lastmod": "2023-10-23 19:40:00", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "On the theory of electron, H-atom and proton transfers", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 1984.\n\nIt is a pleasure to acknowledge the support of this research by the Office of Naval Research. Contribution No. 6856.\n\nPublished - 392308.pdf
", "abstract": "The initial part of this article discusses some recent\nexperiments on electron transfer reactions and comments\non the related theory, including the frequency of solvent\nfluctuations. Also described are recent advances with\nBabamov and Lopex on the dynamics of H-atom transfer\nreactions. We then outline the application of the basic idea\nto H and W transfers in complex systems and in condensed\nphases (fast H-coordinates, slow remaining coordinates).\nSimilarities and differences between electron transfers and\nH or W transfers are next described. The relation of the\npresent theory of such transfers to conventional transition\nstate theory is discussed.", "date": "1984", "date_type": "published", "publisher": "Electrochemical Society", "place_of_pub": "Pennington, NJ", "pagerange": "169-186", "id_number": "CaltechAUTHORS:20150701-085945205", "isbn": "9780835725910", "book_title": "The Chemistry and Physics of Electrocatalysis", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-085945205", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" } ] }, "other_numbering_system": { "items": [ { "id": "6856", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "McIntyre-J-D-E", "name": { "family": "McIntyre", "given": "J. D. E." } }, { "id": "Weaver-M-J", "name": { "family": "Weaver", "given": "M. J." } }, { "id": "Yeager-E-B", "name": { "family": "Yeager", "given": "E. B." } } ] }, "primary_object": { "basename": "392308.pdf", "url": "https://authors.library.caltech.edu/records/mr05x-kz788/files/392308.pdf" }, "resource_type": "book_section", "pub_year": "1984", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/jd0af-55103", "eprint_id": 58732, "eprint_status": "archive", "datestamp": "2023-08-19 15:38:07", "lastmod": "2023-10-23 19:40:21", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Vibrational Motion in the Regular and Chaotic Regimes, Classical and Quantum Mechanics", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1983 Springer. \n\nThis research was supported in part by the National Science\nFoundation. I am particularly indebted to my co-workers, Don Noid and Michael Koszykowski, for many helpful discussions. This article is Contribution No. 6381 from the California Institute of Technology.", "abstract": "There are many experiments which are related to intramolecular energy transfer. Initially, they involved primarily thermal unimolecular reactions and chemical activation. More recently, experiments which are more state-selective have also been performed in which one zeroth order mode (e.g., some bond or normal mode) has been excited. These experiments include infrared multiphoton absorption, reactions induced by excitation of high CH overtones, dissociation of vibrational state-excited van der Waals' complexes, and fluorescence spectra from mode-selected vibrationally-excited substituted aromatic molecules.", "date": "1983", "date_type": "published", "publisher": "Springer-Verlag", "place_of_pub": "New York, NY", "pagerange": "573-583", "id_number": "CaltechAUTHORS:20150701-102136981", "isbn": "978-1-4613-3669-3", "book_title": "Energy Storage and Redistribution in Molecules", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-102136981", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "6381", "name": "Caltech Department of Chemistry" } ] }, "contributors": { "items": [ { "id": "Hinze-J", "name": { "family": "Hinze", "given": "Juergen" } } ] }, "doi": "10.1007/978-1-4613-3667-9_31", "resource_type": "book_section", "pub_year": "1983", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/2sd09-hb554", "eprint_id": 58738, "eprint_status": "archive", "datestamp": "2023-08-19 15:19:45", "lastmod": "2024-01-13 16:23:24", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Siders-P", "name": { "family": "Siders", "given": "Paul" } } ] }, "title": "Further Developments in Electron Transfer", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1982 American Chemical Society. Received April 21, 1982. Publication Date (Print): July 23, 2009.\n\nIt is a pleasure to acknowledge support of this research by\na grant from the National Science Foundation. Contribution No. 6494 from the California Institute of Technology.", "abstract": "The inverted region in electron transfer reactions is studied for the reaction of electronically-excited ruthenium(II) tris-bipyridyl ions with various metal(III) tris-bipyridyl complexes. Numerical calculations for the diffusion-reaction equation are summarized for the case where electron transfer occurs over a range of distances. Comparison is made with the experimental data and with a simple approximation. The analysis reveals some of the factors which can cause a flattening of the ln k_(obs) versus \u0394G^O curve in the inverted region. Ways of improving the chance of observing the effect are discussed.", "date": "1982-09-27", "date_type": "published", "publisher": "American Chemical Society", "place_of_pub": "Washington, DC", "pagerange": "235-253", "id_number": "CaltechAUTHORS:20150701-132931351", "isbn": "9780841207349", "book_title": "Mechanistic Aspects of Inorganic Reactions", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-132931351", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "6494", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Endicott-J-F", "name": { "family": "Endicott", "given": "John F." } }, { "id": "Rorabacher-D-B", "name": { "family": "Rorabacher", "given": "David B." } } ] }, "doi": "10.1021/bk-1982-0198.ch010", "resource_type": "book_section", "pub_year": "1982", "author_list": "Marcus, R. A. and Siders, Paul" }, { "id": "https://authors.library.caltech.edu/records/63trc-01j27", "eprint_id": 58733, "eprint_status": "archive", "datestamp": "2023-08-19 14:43:05", "lastmod": "2023-10-23 19:40:26", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "On Quantum, Classical and Semiclassical Calculations of Electron Transfer Rates", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1982 Pergamon, New York, 1982. \n\nIt is a pleasure to acknowledge support of this research by a grant from the National Science Foundation. Contribution No. 6128 from the Arthur Ames Noyes Laboratory of Chemical Physics, California Institute of Technology.", "abstract": "Similarities and differences between quantum, semiclassical and classical treatments of electron transfer reactions are described. All of these methods can be described as \"vibrationally assisted electron-tunneling.\" A simple approximate expression is given for an infinite sum of Bessel functions which appears in the nonadiabatic quantum description. The condition of its validity is also obtained.\nThe expression has been tested for some systems when the frequencies contain those in the range of the usual metal - ligand frequencies (~450 cm^(-1)> and of the low frequencies of the environment. The nonadiabatic classical expression provides a useful lower bound, because it has no nuclear tunneling, to the nonadiabatic quantum result. The quantum correction is calculated for some actual systems. The \"semiclassical\" approximation is sometimes larger and sometimes smaller (in the \"normal\" and \"inverted\" regions,\nrespectively) than the quantum result. This behavior is readily understood in terms of WKB theory. The quantum correction to the classical cross-relation of rate constants was calculated for a case of interest and found to be minor. A symmetric form of (lnk, \u0394^0) plots is described, even for the usually skewed quantum plots.", "date": "1982", "date_type": "published", "publisher": "Pergamon Press", "place_of_pub": "New York, NY", "pagerange": "3-19", "id_number": "CaltechAUTHORS:20150701-103436694", "isbn": "9780080244211", "book_title": "Oxidases and Related Redox Systems", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-103436694", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "other_numbering_system": { "items": [ { "id": "6128", "name": "Caltech Arthur Ames Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "King-Tsoo-E", "name": { "family": "King", "given": "Tsoo E." } }, { "id": "Mason-H-S", "name": { "family": "Mason", "given": "Howard S." } }, { "id": "Morrison-M", "name": { "family": "Morrison", "given": "Martin" } } ] }, "doi": "10.1016/B978-0-08-024421-1.50005-7", "resource_type": "book_section", "pub_year": "1982", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/psxdg-pqy81", "eprint_id": 60569, "eprint_status": "archive", "datestamp": "2023-08-19 14:43:18", "lastmod": "2024-01-13 16:25:37", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Unimolecular Processes and Vibrational Energy Randomization", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1982 Springer.\n\nThis work has involved an active and stimulating collaboration with former students, particularly with Drs. Noid and Koszykowski, my co-authors in [1]. This research was supported by a grant from the National Science Foundation.", "abstract": "Intramolecular vibrational energy transfer is the subject of much current experimental and theoretical research. Some aspects of this problem are reviewed in this talk, together with a few new additions. Inasmuch as extensive references have been given in a recent review,1 they are omitted in this extended abstract in the interests of brevity. Topics discussed include (1) experimental work, (2) some theoretical concepts on \"regular\" and \"chaotic\" motion in the classical and quantum mechanics of anharmonic systems, and (3) the question of whether experiments can distinguish regular from chaotic behavior. By way of introduction we begin first with a review of the unimolecular rate constant, of reactions occurring in the gas phase.", "date": "1982", "date_type": "published", "publisher": "Springer-Verlag", "place_of_pub": "New York, NY", "pagerange": "254-259", "id_number": "CaltechAUTHORS:20150928-103931001", "isbn": "978-3-642-87866-4", "book_title": "Picosecond Phenomena III", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-103931001", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Eisenthal-K-B", "name": { "family": "Eisenthal", "given": "K. B." } }, { "id": "Hochstrasser-R-M", "name": { "family": "Hochstrasser", "given": "R. M." } }, { "id": "Kaiser-M", "name": { "family": "Kaiser", "given": "M." } }, { "id": "Laubereau-A", "name": { "family": "Laubereau", "given": "A." } } ] }, "doi": "10.1007/978-3-642-87864-0_63", "resource_type": "book_section", "pub_year": "1982", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/k6gmn-1ty96", "eprint_id": 58706, "eprint_status": "archive", "datestamp": "2023-08-19 13:44:47", "lastmod": "2023-10-23 19:38:12", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Ramaswamy-R", "name": { "family": "Ramaswamy", "given": "Ramakrishna" } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Dynamics of forced coupled oscillators: classical phenomenology of infrared multiphoton absorption", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1981 Springer.\n\nWe are pleased to acknowledge the support of this research by\na grant from the National Science Foundation.", "abstract": "The classical mechanics of a system of two nonlinearly coupled oscillators of incommensurate frequencies driven by an oscillating electric field are studied. The presence of quasi-periodic and chaotic motion in the unforced system is shown to influence the nature of energy absorption. Two essentially different types of behavior are observed. In the first, energy is exchanged in a periodic manner between the system and the forcing field. The exact results are compared with perturbative analysis (based on Lie-transform techniques) employed in this regime. In the second regime, the energy exchange is erratic and a statistical analysis of a family of trajectories shows the role of the chaotic motion in the unforced system in the dissociation process. The results of the theory are compared with those obtained from an ensemble of exact classical trajectories and found to be in reasonable agreement.", "date": "1981", "date_type": "published", "publisher": "Springer", "place_of_pub": "Boston, MA", "pagerange": "193-201", "id_number": "CaltechAUTHORS:20150630-112320522", "isbn": "978-1-4613-3258-9", "book_title": "Quantum Mechanics in Mathematics, Chemistry, and Physics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150630-112320522", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Gustafson-K-E", "name": { "family": "Gustafson", "given": "Karl E." } }, { "id": "Reinhardt-W-P", "name": { "family": "Reinhardt", "given": "William P." } } ] }, "doi": "10.1007/978-1-4613-3258-9_14", "resource_type": "book_section", "pub_year": "1981", "author_list": "Ramaswamy, Ramakrishna and Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/2frtd-gsa49", "eprint_id": 58742, "eprint_status": "archive", "datestamp": "2023-08-19 13:44:55", "lastmod": "2023-10-23 19:40:55", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Noid-D-W", "name": { "family": "Noid", "given": "D. W." } }, { "id": "Koszykowski-M-L", "name": { "family": "Koszykowski", "given": "M. L." } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Intramolecular Dynamics in the Quasiperiodic and Stochastic Regimes", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1981 Springer. \n\nWe wish to thank Professor J. D. McDonald at the University of Illinois for many helpful discussions in the early stages of this work. Research sponsored by the U. S. Department of Energy under contract W-7405-eng-26 with the Union Carbide Corporation, and DOE at Sandia National Laboratory, and NSF at California Institute of Technology.", "abstract": "Nonlinear dynamics has been the subject of intense study in recent years. In this review article, we present a summary of our recent work in this field, in which nonlinear dynamics is applied to problems involving molecular behavior. Four aspects are described: (1) semiclassical methods for the calculation of bound-state eigenvalues, (2) classical spectra and correlation functions in the quasiperiodic and \"chaotic\" regimes, (3) \"chaotic\" behavior in quantum mechanics, and (4) applications to collisional and laser interactions.", "date": "1981", "date_type": "published", "publisher": "Springer", "place_of_pub": "Boston, MA", "pagerange": "133-166", "id_number": "CaltechAUTHORS:20150701-134922081", "isbn": "978-1-4613-3260-2", "book_title": "Quantum Mechanics in Mathematics, Chemistry, and Physics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-134922081", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "W-7405-eng-26" }, { "agency": "Union Carbide Corporation" }, { "agency": "Sandia National Laboratory" }, { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Gustafson-K-K", "name": { "family": "Gustafson", "given": "Karl K." } }, { "id": "Reinhardt-W-P", "name": { "family": "Reinhardt", "given": "William P." } } ] }, "doi": "10.1007/978-1-4613-3258-9_10", "resource_type": "book_section", "pub_year": "1981", "author_list": "Noid, D. W.; Koszykowski, M. L.; et el." }, { "id": "https://authors.library.caltech.edu/records/hsaqb-bnp89", "eprint_id": 58580, "eprint_status": "archive", "datestamp": "2023-08-19 12:54:32", "lastmod": "2024-01-13 16:23:09", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Intramolecular Dynamics: Regular and Stochastic Vibrational States of Molecules", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1980 by D. Reidel Publishing Company.\n\nIt is a pleasure to acknowledge the contributions of my coworkers, Drs. M. Tabor, D. M. Noid, M. L. Koszykowski, W.-K. Liu, and R. Ramaswamy and the support of this research by the National Science Foundation. I am particularly indebted to Dr. Tabor for his critical reading of the manuscript and for his very helpful advice. Contribution No. 6145 from the California Institute of Technology.", "abstract": "The nature of molecular vibrational states at low and high energies\nhas been studied both classically and quantum mechanically. At low\nenergies the classical vibrational motion is highly \"regular\" (quasi-periodic)\nin the usual harmonic normal mode regime. Interestingly\nenough, it can still remain so when the motion is anharmonic. However,\nat high enough vibrational energies numerical calculations indicate\nthat the classical mechanical motion usually becomes chaotic (frequently\ntermed \"stochastic\") although still deterministic, of course. The\ncorresponding quantum mechanical behavior is discussed using semi-classical\nideas, and a method of calculating eigenvalues in the quasi-periodic\nregime is described.\nA definition of quantum stochasticity is proposed in terms of\noverlapping avoided crossings in quantum mechanical eigenvalue versus\nperturbation parameter plots. Some implications for phenomena such as\nintramolecular relaxation, spectra, unimolecular reactions, and infrared\nmultiphoton dissociation of molecules are described.", "date": "1980", "date_type": "published", "publisher": "D. Reidel", "place_of_pub": "Dordrecht", "pagerange": "107-121", "id_number": "CaltechAUTHORS:20150624-102015286", "isbn": "9789027711052", "book_title": "Horizons of Quantum Chemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150624-102015286", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "other_numbering_system": { "items": [ { "id": "6145", "name": "Caltech Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Fukui-K", "name": { "family": "Fukui", "given": "K." } }, { "id": "Pullman-B", "name": { "family": "Pullman", "given": "B." } } ] }, "doi": "10.1007/978-94-009-9027-2_10", "resource_type": "book_section", "pub_year": "1980", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/3fg53-wqe48", "eprint_id": 58745, "eprint_status": "archive", "datestamp": "2023-08-19 12:54:37", "lastmod": "2024-01-13 16:23:26", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Similarities and Differences Between Electron and Proton Transfers at Electrodes and in Solution. Theory of a Hydrogen Evolution Reaction", "ispublished": "unpub", "full_text_status": "public", "note": "\u00a9 1980 Electrochemical Society.\n\nContribution No. 6006.\nSupported by a contract from the Office of Naval Research.\n\nPublished - 392321.pdf
", "abstract": "Depending on the initial energies, a proton transfer may\nproceed either via a saddle-point in a potential energy surface or by crossing from the reactants' to the products'\nvalley before the saddle-point is reached. In the second\npath the analogy to weak-overlap electron transfers is\npointed out. The present study is intended to unify previously divergent viewpoints, by showing how they are\nspecial cases of a more general picture. Expressions are\nobtained for the reaction rate in terms of the properties of\nthe potential energy surface and of other properties of the\nsystem, using a hydrogen evolution reaction as an example.", "date": "1980", "date_type": "published", "publisher": "Electrochemical Society", "id_number": "CaltechAUTHORS:20150701-143923667", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150701-143923667", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" } ] }, "other_numbering_system": { "items": [ { "id": "6006", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Bruckenstein-S", "name": { "family": "Bruckenstein", "given": "S." } }, { "id": "McIntyre-J-D-E", "name": { "family": "McIntyre", "given": "J. D. E." } }, { "id": "Miller-B", "name": { "family": "Miller", "given": "B." } }, { "id": "Yeager-E", "name": { "family": "Yeager", "given": "E." } } ] }, "primary_object": { "basename": "392321.pdf", "url": "https://authors.library.caltech.edu/records/3fg53-wqe48/files/392321.pdf" }, "resource_type": "book_section", "pub_year": "1980", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/32647-xyj81", "eprint_id": 60565, "eprint_status": "archive", "datestamp": "2023-08-19 11:53:30", "lastmod": "2024-01-13 16:25:32", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electron Transfer and Tunneling in Chemical and Biological Systems", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1979", "abstract": "Various aspects of electron transfer reactions in\nchemical and biological systems are discussed . They include\nthe role of potential energy surfaces, nuclear tunneling, temperature behavior, thermodynamic factors, relation of the preexponential factor in the rate constant to electron tunneling, the effect of applied electric fields, and charge transfer and other spectra. Classical and quantum equations are given, and the relation between recent and earlier quantum theories is discussed. Several biological reactions are considered with these results in mind, utilizing some information available in chemical systems.", "date": "1979", "date_type": "published", "publisher": "Chemie-Verlag", "place_of_pub": "New York, NY", "pagerange": "15-43", "id_number": "CaltechAUTHORS:20150928-092749302", "isbn": "978-3527120017", "book_title": "Light-Induced Charge Separation in Biology and Chemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-092749302", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "other_numbering_system": { "items": [ { "id": "5867", "name": "Caltech Arthur Amos Noyes Laboratory of Chemical Physics" } ] }, "contributors": { "items": [ { "id": "Gerischer-H", "name": { "family": "Gerischer", "given": "H." } }, { "id": "Katz-J-J", "name": { "family": "Katz", "given": "J. J." } } ] }, "resource_type": "book_section", "pub_year": "1979", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/ae35p-12b62", "eprint_id": 60566, "eprint_status": "archive", "datestamp": "2023-08-19 11:53:37", "lastmod": "2024-01-13 16:25:34", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Joussot-J", "name": { "family": "Joussot", "given": "J." } }, { "id": "Albrecht-R-A-C", "name": { "family": "Albrecht", "given": "Rappoteur A. C." } }, { "id": "Gerischer-H", "name": { "family": "Gerischer", "given": "H." } }, { "id": "Knox-R-S", "name": { "family": "Knox", "given": "R. S." } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Schott-M", "name": { "family": "Schott", "given": "M." } }, { "id": "Weller-A", "name": { "family": "Weller", "given": "A." } }, { "id": "Willig-F", "name": { "family": "Willig", "given": "F." } } ] }, "title": "Mechanisms of Charge Separation and Subsequent Processes Group Report", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1979 Chemie-Verlag.", "abstract": "The theoretical aspects of charge separation were discussed in this group and reexamined, in particular with respect to tunneling (cf. Gr\u00e4tzel et al., this volume). Basically three theories approach the general problem of rate\nreactions and are potentially applicable, among other processes, to electron, proton , or H-atom transfer, as long as these are \"one step\" processes. The best known treatment and the most widely referred to in the literature (because it is best understood by the experimentalist) is the one elaborated by Marcus (15). This theory is considered classical because the nuclear\nmotions are treated on a classical basis, quantum mechanics\nbeing applied to the electron motion.", "date": "1979", "date_type": "published", "publisher": "Chemie-Verlag", "place_of_pub": "New York, NY", "pagerange": "129-149", "id_number": "CaltechAUTHORS:20150928-100912453", "isbn": "978-3527120017", "book_title": "Light-Induced Charge Separation in Biology and Chemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-100912453", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "Gerischer-H", "name": { "family": "Gerischer", "given": "Heinz" } }, { "id": "Katz-J-J", "name": { "family": "Katz", "given": "J. J." } } ] }, "resource_type": "book_section", "pub_year": "1979", "author_list": "Joussot, J.; Albrecht, Rappoteur A. C.; et el." }, { "id": "https://authors.library.caltech.edu/records/cv5k8-04758", "eprint_id": 60556, "eprint_status": "archive", "datestamp": "2023-08-19 11:53:22", "lastmod": "2024-01-13 16:25:30", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Noid-D-W", "name": { "family": "Noid", "given": "D. W." } }, { "id": "Koszykowski-M-L", "name": { "family": "Koszykowski", "given": "M. L." } } ] }, "title": "Semiclassical studies of bound states and molecular dynamics", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1979 Springer. \n\nThis research was supported by the National Science Foundation. Some of the wave functions were computed at Oak Ridge National Laboratory. We are pleased to acknowledge, too, discussions with Professor E. Atlee Jackson.", "abstract": "Semiclassical studies on molecular bound states, molecular collisions, and time-dependent dynamical systems are described. Several methods have been evolved for determining the action variables of nonseparable bound state systems, and thereby for calculating their quantum mechanical eigenvalues. Nonresonant and resonant systems are included, and surfaces of section in higher (>2) dimensional as well as in two-dimensional systems are obtained. Further, from the Fourier transform of an autocorrelation function the molecular spectrum can be determined directly from a trajectory. The effect of an oscillating electric field on a molecule is discussed semiclassically with a view to obtaining a relation between the classical mechanical and quantum mechanical treatments.", "date": "1979", "date_type": "published", "publisher": "Springer", "place_of_pub": "New York, NY", "pagerange": "283-392", "id_number": "CaltechAUTHORS:20150928-075703324", "isbn": "978-3-540-09120-2", "book_title": "Stochastic Behavior in Classical and Quantum Hamiltonian Systems", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-075703324", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Casati-G", "name": { "family": "Casati", "given": "Giulio" } }, { "id": "Ford-J", "name": { "family": "Ford", "given": "Joseph" } } ] }, "doi": "10.1007/BFb0021751", "resource_type": "book_section", "pub_year": "1979", "author_list": "Marcus, R. A.; Noid, D. W.; et el." }, { "id": "https://authors.library.caltech.edu/records/80rgs-wyr94", "eprint_id": 60567, "eprint_status": "archive", "datestamp": "2023-08-19 11:16:41", "lastmod": "2024-01-13 16:25:35", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Noid-D-W", "name": { "family": "Noid", "given": "D. W." } }, { "id": "Koszykowski-M-L", "name": { "family": "Koszykowski", "given": "M. L." } } ] }, "title": "Energy Redistribution in Molecules in the Quasi-Periodic and Ergodic Regimes", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1978 Springer.\n\nWe are pleased to acknowledge the support of the research by the National Science Foundation. We are also indebted to Dr. Michael Tabor for helpful discussions.", "abstract": "Some results on the classical mechanics of anharmonic vibrations in several-dimensional systems are summarized, and their relation to unimolecular reaction rate theory and to infrared multiphoton dissociation of molecules is discussed. Quantum connections are considered using semiclassical theory.", "date": "1978-03", "date_type": "published", "publisher": "Springer-Verlag", "place_of_pub": "New York, NY", "pagerange": "298-307", "id_number": "CaltechAUTHORS:20150928-102511011", "isbn": "978-3-642-67056-5", "book_title": "Advances in Laser Chemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-102511011", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Zewail-A-H", "name": { "family": "Zewail", "given": "Ahmed H." } } ] }, "doi": "10.1007/978-3-642-67054-1_29", "resource_type": "book_section", "pub_year": "1978", "author_list": "Marcus, R. A.; Noid, D. W.; et el." }, { "id": "https://authors.library.caltech.edu/records/rgkrp-96g34", "eprint_id": 60577, "eprint_status": "archive", "datestamp": "2023-08-19 10:50:33", "lastmod": "2023-10-24 16:41:22", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theories of electrode kinetics", "ispublished": "unpub", "full_text_status": "restricted", "keywords": "Electrodes, Electron Transfer, Protons, Reaction Kinetics, Electron Transitions, Ions, Metals, Potential Energy, Surface Reactions", "note": "\u00a9 1977.\n\nIt is a pleasure to acknowledge the support of this research by the Office of Naval Research.", "abstract": "The present lecture consists of two parts. In the first, a comparison is made of theory and experiment for simple electron transfer reactions in solution and at electrodes, reactions for which no bonds are broken of formed. The main part of the lecture is concerned with electrode reactions involving the breaking and forming of chemical bonds and principally with the hydronium ion discharge reaction, H_3O(+) + M(e) yields H_2O + H-M(ads.). The treatment of this reaction has been the subject of some controversy (cf. 1965 Faraday Discussions on Proton Transfer and more recent literature). To provide further insight, a more dynamical theory of this elementary step for general potential energy surfaces is described. It is then shown how, depending on the nature of the potential energy surface, the theory leads to various approaches in the literature. For example, depending on the surface, the system may or may not for dynamical reasons be able to reach sufficiently easily the saddle-point region or, again, Franck-Condon solvation effects may or may not contribute to the rate. There is a clear need for the application of recent theoretical methods of electronic structure to determine the essential features of the potential energy surface.", "date": "1977-09", "date_type": "published", "publisher": "Advance Publications Ltd.", "place_of_pub": "London", "pagerange": "473-482", "id_number": "CaltechAUTHORS:20150928-124501792", "isbn": "0-903012-40-5", "book_title": "Proceedings of the Conference on Physicochemical Hydrodynamics", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-124501792", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Spalding-D-B", "name": { "family": "Spalding", "given": "D. Brian" } }, { "id": "Levich-V-G", "name": { "family": "Levich", "given": "Veniamin Grigor'evich" } } ] }, "resource_type": "book_section", "pub_year": "1977", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/ayj6m-sds52", "eprint_id": 60593, "eprint_status": "archive", "datestamp": "2023-08-19 10:41:14", "lastmod": "2023-10-24 16:42:28", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electrostatic Free Energy and Other Properties of States Having Nonequilibrium Polarization. II. Electrode Systems", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1977 Elsevier. \n\nOffice of Naval Research, Technical Report No. 11, Contract Nonr 839(09), Task No. NR 051-339.", "abstract": "In certain electrode processes involving electron transfer mechanisms, a portion of the dielectric polarization is not in electrostatic equilibrium with the charge distribution. In the present paper expressions are deduced for the properties of such systems. These properties include the electrostatic free energy, entropy and energy, and the spatial dependence of the inner potential. The method of images provides a convenient means for determining the electrode charge distribution, due account being taken of its quantum limitations. These expressions have been used to formulate a quantitative theory of overvoltage for electron transfer electrode processes.", "date": "1977-06", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "New York, NY", "pagerange": "210-224", "id_number": "CaltechAUTHORS:20150929-101229996", "isbn": "978-0444416278", "book_title": "Special Topics in Electrochemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150929-101229996", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)", "grant_number": "Nonr 839(09)" } ] }, "contributors": { "items": [ { "id": "Rock-P-A", "name": { "family": "Rock", "given": "Peter A." } } ] }, "resource_type": "book_section", "pub_year": "1977", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/6q3s6-2hv45", "eprint_id": 60585, "eprint_status": "archive", "datestamp": "2023-08-19 10:40:59", "lastmod": "2023-10-24 16:41:45", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "On the Theory of Overvoltage for Electrode Processes Possess ing Electron Transfer Mechanisms. I.", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1977 Elsevier.", "abstract": "The following article was first prepared as the above Office of Naval Research Technical Report, and is being reproduced here in its entirety. The results were applied in subsequent papers on electrode kinetics [I], and the Report itself has been widely cited in the literature.\nOriginally intended for journal publication, the article was never submitted because of the efforts of the author towards generalization. The generalization was published some years later [2], but in some respects the approach of the 1957 Technical Report is more readable. The principal\ngeneralizations are the inclusion of inner coordination shell contributions and the use of statistical mechanics for inner and outer contributions [2,3]. The 1957 Report and a predecessor [4] had as their aims the treatment of the outer shell contribution; their equation for the dielectric continuum calculation of that contribution is the same as that in the later publication [2]. The Report draws upon some derivations in ONR Technical Report No.11, and this latter Report is included also. The generalization\nof those results may be found in Ref. [5]. Elsewhere in this book we comment on more recent developments.", "date": "1977-06", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "New York, NY", "pagerange": "180-209", "id_number": "CaltechAUTHORS:20150928-152056871", "isbn": "978-0444416278", "book_title": "Special Topics in Electrochemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-152056871", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "Rock-P-A", "name": { "family": "Rock", "given": "Peter A." } } ] }, "resource_type": "book_section", "pub_year": "1977", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/88sby-wq994", "eprint_id": 60591, "eprint_status": "archive", "datestamp": "2023-08-19 10:41:06", "lastmod": "2023-10-24 16:42:18", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theory and Applications of Electron Transfer at Electrodes and in Solution", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1977 Elsevier. \n\nThe author is pleased to acknowledge the support of this work by the Office of Naval Research.", "abstract": "The theory of simple electron transfers at electrodes and in solution is reviewed, and various thermal fluctuations of coordinates leading to electron transfer are described. A simplified derivation is given of the free energy of such fluctuations. Implications of the theoretical equations\nfor experiment are described, some of t relevant results having been summarized recently in Dahlem Konferenz Phys. Chem. Sci. Res. Rept., 1(1975)477. They include relations between rate constants of cross-reactions and self-exchange reactions, between rates of reactions at electrodes and those in solution, nonspecific solvent effects, chemiluminescence, and other properties. Approximate equations of the BEBO type are also given for Tafel slopes, Bronsted slopes and rates of cross-reactions, for systems involving rupture and formation of bonds.", "date": "1977-06", "date_type": "published", "publisher": "Elsevier", "place_of_pub": "New York, NY", "pagerange": "161-179", "id_number": "CaltechAUTHORS:20150929-092634191", "isbn": "978-0444416278", "book_title": "Special Topics in Electrochemistry", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150929-092634191", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)" } ] }, "contributors": { "items": [ { "id": "Rock-P-A", "name": { "family": "Rock", "given": "Peter A." } } ] }, "resource_type": "book_section", "pub_year": "1977", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/a08ap-t2281", "eprint_id": 60586, "eprint_status": "archive", "datestamp": "2023-08-19 09:13:12", "lastmod": "2024-01-13 16:25:41", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Electron Transfer in Homogeneous and Heterogeneous Systems", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1975 Berlin, Germany.", "abstract": "The mechanism o f electron transfer in solution and\nat electrodes is described. A theoretical analysis involving\nthe fluctuations in the chemical bond distances and in the dielectric polarization of the partially oriented solvent molecules about the reactants leads to an expression for the rate constant of these reactions. Relations are obtained between the rate constants of cross reactions k_(12) self-exchange reactions k_(11), [e.g., k_(12)\u2245 (k_(11)k_(22)K_(12)f_(12)1/2, and reactions at surfaces (electrodes, both metal and semiconductor type). There are many comparisons between theory and experiment and a survey is given. The effect of standard free energy of reaction and of electrode potential is included, as in the Co^(+3) (aq) anomaly, and the occurrence of chemiluminescence. The discussion is preceded by a brief description of reaction rate theory in general and of atom versus electron transfer mechanisms in particular.", "date": "1975", "date_type": "published", "publisher": "Phys Chem Sci Res Rep", "place_of_pub": "Berlin, Germany", "pagerange": "477-504", "id_number": "CaltechAUTHORS:20150929-075236138", "isbn": "978-3820012019", "book_title": "The Nature of Seawater", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150929-075236138", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "Goldberg-E-D", "name": { "family": "Goldberg", "given": "Edward D." } }, { "id": "Edmond-J-M", "name": { "family": "Edmond", "given": "John M." } } ] }, "resource_type": "book_section", "pub_year": "1975", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/9sdx4-3jb04", "eprint_id": 60572, "eprint_status": "archive", "datestamp": "2023-08-19 09:13:05", "lastmod": "2024-01-13 16:25:39", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Rapporteur-P-S-L", "name": { "family": "Rapporteur", "given": "P. S. Liss" } }, { "id": "Betine-K", "name": { "family": "Bertine", "given": "K." } }, { "id": "Clearfield-A", "name": { "family": "Clearfield", "given": "A." } }, { "id": "Kratohvil-J", "name": { "family": "Kratohvil", "given": "J." } }, { "id": "Lyklema-J", "name": { "family": "Lyklema", "given": "J." } }, { "id": "MacIntyre-F", "name": { "family": "MacIntyre", "given": "F." } }, { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" }, { "id": "Martin-J-M", "name": { "family": "Martin", "given": "J. M." } }, { "id": "Morrison-G-H", "name": { "family": "Morrison", "given": "G. H." } }, { "id": "Nancollas-G-H", "name": { "family": "Nancollas", "given": "G. H." } }, { "id": "Ottewill-R-H", "name": { "family": "Ottewill", "given": "R. H." } }, { "id": "Parsons-R", "name": { "family": "Parsons", "given": "R." } }, { "id": "Pravdi\u0107-V", "name": { "family": "Pravdi\u0107", "given": "V." } }, { "id": "Sherry-H-S", "name": { "family": "Sherry", "given": "H. S." } } ] }, "title": "The Colloidal State and Surface Phenomena - Group Report", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1975.", "abstract": "Seawater contains particles, both inorganic and biologically produced, ranging in size from colloidal to those which will settle under gravity. The concentration of particulates matter in any part of the oceans depends on the proximity and magnitude of inputs of solid material. Such sources can be both external (atmosphere, land masses, marine sediments) an internal, which includes particles formed biologically as well as those produced by bubbling, precipitation, etc.", "date": "1975", "date_type": "published", "publisher": "Dahlem Konferenzen", "place_of_pub": "Berlin, Germany", "pagerange": "453-475", "id_number": "CaltechAUTHORS:20150928-105714500", "isbn": "9783820012019", "book_title": "The Nature of Seawater", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150928-105714500", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "contributors": { "items": [ { "id": "Goldberg-E-D", "name": { "family": "Goldberg", "given": "Edward D." } }, { "id": "Edmond-J-M", "name": { "family": "Edmond", "given": "John M." } } ] }, "resource_type": "book_section", "pub_year": "1975", "author_list": "Rapporteur, P. S. Liss; Bertine, K.; et el." }, { "id": "https://authors.library.caltech.edu/records/xv3z7-jhd35", "eprint_id": 56535, "eprint_status": "archive", "datestamp": "2023-08-19 08:42:44", "lastmod": "2024-01-13 16:17:28", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Activated-complex theory: current status, extensions, and applications", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1974 Wiley. \n\nI am particularly indebted to my co-worker, Dr. Richard Ellis, for his helpful comments. Research on which some of the material in this chapter was based was supported by a grant from the National Science Foundation.", "abstract": "The activated-complex theory of chemical reactions has proved to be very\nuseful in interpreting rate data on a wide variety of chemical reactions. The\ntopics so treated include preexponential factors of bimolecular gas-phase\nreactions, preexponential factors at high pressures of unimolecular reactions, salt and polar solvent effects on bimolecular-reaction rates, and recombination\nrates of radicals under certain conditions. In conjunction with additional\nconcepts, the theory has also found extensive use in such subjects as pressure\neffects on unimolecular reactions (so-called RRKM theory}, chemical\nactivation, and electron-transfer reactions both in solution and at electrodes.\nIn the present chapter the assumptions and several derivations of the\ntheory are considered. Some of the recent tests of activated-complex theory\nthat are based on the numerical solution of the dynamical equations of\nmotion of the reactants are summarized. Topics such as the \"free-energy-maximization\ncriterion\" for the position of the activated complex are also\nconsidered. Several of the applications of activated-complex theory are\ntreated, and some dynamical extensions of it are noted.\nSome of the work described in the present chapter is drawn from the\nwriter's published studies, but the material in Sections 3 and 5 on an ensemble\nderivation for reactions in solution and on a basis for the usual\nfree-energy-maximization criterion for location of the activated complex is\ndrawn from unpublished work.", "date": "1974", "date_type": "published", "publisher": "Wiley", "place_of_pub": "New York, NY", "pagerange": "13-46", "id_number": "CaltechAUTHORS:20150409-123823320", "isbn": "9780471930952", "book_title": "Investigation of rates and mechanisms of reactions, 3rd ed.", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150409-123823320", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Hammes-G-G", "name": { "family": "Hammes", "given": "G. G." } } ] }, "resource_type": "book_section", "pub_year": "1974", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/3me0j-ph285", "eprint_id": 60603, "eprint_status": "archive", "datestamp": "2023-08-19 05:04:09", "lastmod": "2024-01-13 16:25:43", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theoretical Study of Electron Transfer Reactions of Solvated Electrons", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1965 American Chemical Society. \n\nReceived May 3, 1965. \n\nSupported by a grant from the National Science Foundation.", "abstract": "The assumptions, equations and several applications of a recently formulated theory of electron transfer reactions of solvated electrons are outlined. The relationship of the reorganization terms to those of ordinary electron exchange and electrochemical reactions is described, together with the role played by an effective standard free energy of reaction. Applications include prediction of conditions under which chemiluminescence might be found and description of conditions under which reactions might not be diffusion-controlled.", "date": "1965-07-22", "date_type": "published", "publisher": "American Chemical Society", "place_of_pub": "Washington, DC", "pagerange": "138-148", "id_number": "CaltechAUTHORS:20150930-101029562", "isbn": "9780841200517", "book_title": "Solvated Electron", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150930-101029562", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "contributors": { "items": [ { "id": "Hart-E-J", "name": { "family": "Hart", "given": "Edwin J." } } ] }, "doi": "10.1021/ba-1965-0050.ch011", "resource_type": "book_section", "pub_year": "1965", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/b4wwd-wmk29", "eprint_id": 60604, "eprint_status": "archive", "datestamp": "2023-08-19 04:55:06", "lastmod": "2023-10-24 16:43:18", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "Theory of Electron-Transfer Reactions and of Related Phenomena", "ispublished": "unpub", "full_text_status": "restricted", "abstract": "Data on electron exchange reactions have provided insight into factors influencing rates of electron-transfer reactions in solution. The present paper has the twofold purpose of discussing some of these factors and of describing applications of these exchange data and theory to other phenomena. The reaction rate depends upon the extent of reorganization of bond lengths (angles) in the reactants and of solvent reorientation outside them. The reorganization is facilitated or hindered in a comparatively simple way by a favorable or unfavorable standard free energy of reaction. The rate depends, too, on coulombic and other interactions, as evidenced perhaps by certain salt effects, though probably only by a few orders of magnitude typically. The observed variation of rates of some 15 orders of magnitude is best attributed primarily 10\ndifferences in the vibrational reorganization term, a factor calculable from bond lengths and force constants\nwhen known. A remaining factor, non-adiabaticity, is at present of uncertain importance. Arrhenius frequency\nfactors in chemical and electrochemical exchange rate constants would provide the most direct information,\nbut can be complicated or even dwarfed by solvent reordering effects in the coulombic interaction. Available\ndata are few. They provide examples where a non-adiabatic effect is minor. There appear to be no known examples where it is major (Fe2+ - Fe3+ could be a candidate but its mechanism is apparently uncertain). Reorganization in reactants and in solvent occurs in a variety of related phenomena, and related concepts will be applied to treat them. In turn, chemical exchange data have useful applications to the latter. These areas include electrochemical exchange reactions, chemiluminescent electron-transfer reactions (between positive and negative aromatic ions, for example), and redox reactions of the solvated electron. An explanation for the chemiluminescent reactions will be based on the possible \"inverse \u0394F\" effect, discussed several years ago by the author. A related phenomenon involving solvent \"orientation strain\" occurs in light absorption or emission by polar solutes in polar solvents, and the theoretical approach used by the author for treating it is closely related to that used for the exchange reactions.", "date": "1965", "date_type": "published", "publisher": "International Atomic Energy Agency", "id_number": "CaltechAUTHORS:20150930-102431310", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150930-102431310", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "resource_type": "book_section", "pub_year": "1965", "author_list": "Marcus, R. A." }, { "id": "https://authors.library.caltech.edu/records/4yh37-d3p76", "eprint_id": 60605, "eprint_status": "archive", "datestamp": "2023-08-19 03:49:54", "lastmod": "2024-01-13 16:25:45", "type": "book_section", "metadata_visibility": "show", "creators": { "items": [ { "id": "Marcus-R-A", "name": { "family": "Marcus", "given": "R. A." }, "orcid": "0000-0001-6547-1469" } ] }, "title": "A Theory of Electron Transfer Processes at Electrodes", "ispublished": "unpub", "full_text_status": "restricted", "note": "\u00a9 1961 Wiley.\n\nSupported by the Office of Naval Research under Project NR-051-400", "abstract": "Chemical and electrochemical redox reactions have many characteristics in common from the point\nof view of the experimental results and theory. A quantitative theory of the rates of electron transfer\nreactions in solution has been formulated (1) and related concepts used to develop an analogous treatment\nof electrode processes (2). In this chapter we consider the foundations of this theory, their relation\nto quantum mechanical principles, and the relation between the electron transfer mechanism and\nother mechanisms of electrode processes. The quantitative development has been presented elsewhere\n(2). The theoretical equations themselves have been used to interpret some of the data (3). In the\ninterpretation, the relation to chemical electron transfers has been emphasized.", "date": "1961-05", "date_type": "published", "publisher": "Wiley", "id_number": "CaltechAUTHORS:20150930-113133655", "official_url": "https://resolver.caltech.edu/CaltechAUTHORS:20150930-113133655", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Office of Naval Research (ONR)", "grant_number": "NR-051-400" } ] }, "contributors": { "items": [ { "id": "Yeager-E-B", "name": { "family": "Yeager", "given": "Ernest B." } } ] }, "resource_type": "book_section", "pub_year": "1961", "author_list": "Marcus, R. A." } ]