[ { "id": "https://thesis.library.caltech.edu/id/eprint/6779", "eprint_id": 6779, "rev_number": 23, "documents": [ { "id": "/id/document/14094", "doc_id": 14094, "rev_number": 5, "files": [ { "id": "/id/file/90822", "fileid": 90822, "datasetid": "document", "objectid": 14094, "filename": "Belitsky_jm_2002.pdf", "mime_type": "application/pdf", "filesize": 49802669, "mtime": "2012-12-26 04:39:52", "url": "/6779/1/Belitsky_jm_2002.pdf" } ], "eprint_id": 6779, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Belitsky_jm_2002.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/27771" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/27771" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/27771" } ] } }, { "id": "/id/document/14095", "doc_id": 14095, "rev_number": 3, "files": [ { "id": "/id/file/207691", "fileid": 207691, "datasetid": "document", "objectid": 14095, "filename": "Belitsky_jm_2002.zip", "mime_type": "application/zip", "filesize": 167775356, "mtime": "2016-08-22 21:23:30", "url": "/6779/2/Belitsky_jm_2002.zip" } ], "eprint_id": 6779, "pos": 2, "format": "application/zip", "format_desc": "TIFF", "language": "en", "security": "internal", "license": "other", "main": "Belitsky_jm_2002.zip", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final" }, { "id": "/id/document/27771", "doc_id": 27771, "rev_number": 3, "files": [ { "id": "/id/file/90820", "fileid": 90820, "datasetid": "document", "objectid": 27771, "filename": "preview.png", "mime_type": "image/png", "hash": "359ade90a492719d9087bed9748949de", "hash_type": "MD5", "filesize": 23128, "mtime": "2012-12-26 04:39:52", "url": "/6779/3/preview.png" } ], "eprint_id": 6779, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14094" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/14094" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14094" } ] } }, { "id": "/id/document/127156", "doc_id": 127156, "rev_number": 1, "files": [ { "id": "/id/file/372590", "fileid": 372590, "datasetid": "document", "objectid": 127156, "filename": "indexcodes.txt", "mime_type": "text/x-c", "hash": "1b6017db940ac0772778a6291f33fa94", "hash_type": "MD5", "filesize": 38470, "mtime": "2021-06-24 01:29:54", "url": "/6779/4/indexcodes.txt" } ], "eprint_id": 6779, "pos": 4, "placement": 4, "mime_type": "text/x-c", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14094" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14094" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/14094" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/67/79", "datestamp": "2012-01-25 23:30:55", "lastmod": "2021-11-12 23:52:44", "status_changed": "2012-01-25 23:30:55", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Belitsky-Jason-Matthew", "name": { "family": "Belitsky", "given": "Jason Matthew" }, "show_email": "NO" } ] }, "title": "DNA Binding Polyamides in Biological Systems", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Small molecules that bind selectively to a DNA sequence in the human genome are potentially useful tools for molecular biology and human medicine. Polyamides containing\r\nN-methylimidazole (Im) and N-methylpyrrole (Py) are small molecules that bind DNA according to a set of \"pairing rules\" with affinities and specificities that rival natural transcription factors. By directly competing with a given transcription factor or other DNA binding protein for its binding site, polyamide can cause inhibition of diverse biological processes, such as retroviral integration and gene transcription. Polyamides are presented which inhibit the in vitro integration activities for two retroviruses, M-MuLV and HIV-l. Polyamides are described that inhibit TBP binding to the HER2 promoter, a gene implicated in human breast cancer. Failure to achieve inhibition of HER2 transcription in cell culture led to the surprising discovery that polyamide-fluorescent dye conjugates are cell permeable, but that nuclear localization does not occur in many cell lines. Efforts toward modified polyamides with enhanced nuclear localization properties are presented. In order to extend the number of sequences amenable to high affinity recognition, alteration of the C-terminal polyamide tail has been investigated. The development of conditions for polyamide solid-phase synthesis on a new resin, which allows for the generation of \"truncated tail\" polyamides, is presented. During the original route to one of these compounds, an\r\nunexpected reaction was uncovered that leads to entirely different C-terminal tails.", "date": "2002", "date_type": "degree", "id_number": "CaltechTHESIS:01252012-151300693", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01252012-151300693", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2012-01-25 23:30:55", "doi": "10.7907/WNV6-DH45", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Roberts-R-W", "name": { "family": "Roberts", "given": "Richard W." }, "role": "chair" }, { "id": "Dervan-P-B", "name": { "family": "Dervan", "given": "Peter B." }, "orcid": "0000-0001-8852-7306", "role": "chair" }, { "id": "Rees-D-C", "name": { "family": "Rees", "given": "Douglas C." }, "orcid": "0000-0003-4073-1185", "role": "member" }, { "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2002-05-21", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2002", "author_list": "Belitsky, Jason Matthew", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Roberts, Richard W.; Dervan, Peter B.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/4106", "eprint_id": 4106, "rev_number": 19, "documents": [ { "id": "/id/document/6787", "doc_id": 6787, "rev_number": 3, "files": [ { "id": "/id/file/41151", "fileid": 41151, "datasetid": "document", "objectid": 6787, "filename": "thesis.pdf", "mime_type": "application/pdf", "filesize": 40626495, "mtime": "2012-12-26 03:05:28", "url": "/4106/1/thesis.pdf" } ], "eprint_id": 4106, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "thesis.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/23319" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/23319" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/23319" } ] } }, { "id": "/id/document/23319", "doc_id": 23319, "rev_number": 2, "files": [ { "id": "/id/file/41149", "fileid": 41149, "datasetid": "document", "objectid": 23319, "filename": "preview.png", "mime_type": "image/png", "hash": "679c59935ca5e8fe12b2bb3f57d9e72a", "hash_type": "MD5", "filesize": 13211, "mtime": "2012-12-26 03:05:28", "url": "/4106/2/preview.png" } ], "eprint_id": 4106, "pos": 2, "placement": 2, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/6787" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/6787" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/6787" } ] } }, { "id": "/id/document/123995", "doc_id": 123995, "rev_number": 1, "files": [ { "id": "/id/file/369425", "fileid": 369425, "datasetid": "document", "objectid": 123995, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "5360eb58832cc50897d264e1d960ee25", "hash_type": "MD5", "filesize": 66877, "mtime": "2021-06-23 23:12:58", "url": "/4106/3/indexcodes.txt" } ], "eprint_id": 4106, "pos": 3, "placement": 3, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "public", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/6787" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/6787" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/6787" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/41/06", "datestamp": "2001-10-22", "lastmod": "2021-11-05 20:04:17", "status_changed": "2009-09-25 03:11:39", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "adam@astro.ucla.edu", "id": "Burgasser-Adam-Jonathan", "name": { "family": "Burgasser", "given": "Adam Jonathan" }, "orcid": "0000-0002-6523-9536", "show_email": "YES" } ] }, "title": "The Discovery and Characterization of Methane-bearing Brown Dwarfs and the Definition of the T Spectral Class", "ispublished": "unpub", "full_text_status": "public", "keywords": "brown dwarfs; infrared spectroscopy; L dwarfs; low-mass stars; spectral classification; stellar populations; T dwarfs", "abstract": "
I present the discovery of 18 T dwarfs, brown dwarfs exhibiting CH4 absorption analogous to Gliese 229B, identified in the Two Micron All Sky Survey. Follow-up spectroscopic observations reveal the presence of strong H2O and CH4 bands in these objects, as well as broadened Na I and K I absorption in the red optical; fine lines of K I, Cs I, and Rb I; and FeH absorption at 9896 \u00ae Three objects are analyzed in detail; the widely-separated companion brown dwarf Gliese 570D, the coolest known brown dwarf with Teff = 810+/-45 K; the active T dwarf 2MASS 1237+6526, whose unique and steady H alpha emission may be the result of Roche-lobe overflow accretion from a closely-separated companion; and 2MASS 0559-1404, the brightest T dwarf currently known, which appears to be overluminous but unresolved in HST images. The variation in spectral features amongst these objects and those identified by the Sloan Digital Sky Survey have been used to derive a near-infrared spectral classification scheme, tied to the observed strengths of H2O and CH4 bands, color ratios, and K-band spectral morphology. The grid of subclasses segregates the currently known population into seven distinct groups, ranging from T1 V to T8 V. I show that the possible presence of CH4 in the L7 V DENIS 0205-1159AB argues for few subtypes between the latest known L dwarfs and the earliest T dwarfs. One peculiar object, 2MASS 0937+2931, has a highly suppressed K-band peak, likely due to increased H2 opacity in a high-gravity or low-metallicity atmosphere. Examination of absolute brightness and effective temperature across the L/T transition indicates rapid evolution of spectral features, possibly linked to heterogenous cloud coverage as condensibles rain out of the photosphere. Finally, I have used the T dwarf search samples to constrain the substellar field mass function. Through rigorous analysis of selection biases and Monte Carlo simulations, I show that my results are consistent with a power-law mass function scaling as 0.5 [less than] alpha [less than] 1.0, consistent with young stellar cluster surveys but significantly less than current estimates in the field.
", "date": "2002", "date_type": "degree", "id_number": "CaltechETD:etd-10162001-185319", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-10162001-185319", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "local_group": { "items": [ "Astronomy Department" ] }, "deposited_by": "Imported from ETD-db", "deposited_on": "2001-10-22", "doi": "10.7907/KECQ-7R18", "divisions": { "items": [ "div_pma" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" }, { "id": "Porter-F-C", "name": { "family": "Porter", "given": "Frank C." }, "orcid": "0000-0003-1948-8889", "role": "co-advisor" } ] }, "thesis_committee": { "items": [ { "email": "mbrown@gps.caltech.edu", "id": "Brown-M-E", "name": { "family": "Brown", "given": "Michael E." }, "orcid": "0000-0002-8255-0545", "role": "chair" }, { "email": "bts@mop.caltech.edu", "id": "Soifer-B-T", "name": { "family": "Soifer", "given": "B. Thomas" }, "role": "member" }, { "email": "davy@ipac.caltech.edu", "id": "Kirkpatrick-J-D", "name": { "family": "Kirkpatrick", "given": "J. Davy" }, "role": "member" }, { "email": "lah@warning.caltech.edu", "id": "Hillenbrand-L-A", "name": { "family": "Hillenbrand", "given": "Lynne A." }, "role": "member" }, { "email": "pmg@gps.caltech.edu", "id": "Goldreich-P-M", "name": { "family": "Goldreich", "given": "Peter Martin" }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "id": "Porter-F-C", "name": { "family": "Porter", "given": "Frank C." }, "orcid": "0000-0003-1948-8889", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2001-10-16", "thesis_defense_date": "2001-08-24", "thesis_approved_date": "2001-10-22", "review_status": "approved", "option_major": { "items": [ "physics" ] }, "option_minor": { "items": [ "plansci" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained and attached hereto a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2002", "author_list": "Burgasser, Adam Jonathan", "advisor_list": "Janda, Kenneth C. and Porter, Frank C.", "comittee_list": "Brown, Michael E.; Soifer, B. Thomas; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/2129", "eprint_id": 2129, "rev_number": 16, "documents": [ { "id": "/id/document/3876", "doc_id": 3876, "rev_number": 3, "files": [ { "id": "/id/file/22680", "fileid": 22680, "datasetid": "document", "objectid": 3876, "filename": "Aoki_i_2002.pdf", "mime_type": "application/pdf", "filesize": 26641555, "mtime": "2012-12-26 02:47:21", "url": "/2129/1/Aoki_i_2002.pdf" } ], "eprint_id": 2129, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Aoki_i_2002.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/20525" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/20525" }, { "type": 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"media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/10670" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/10670" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/10670" } ] } }, { "id": "/id/document/122155", "doc_id": 122155, "rev_number": 1, "files": [ { "id": "/id/file/367549", "fileid": 367549, "datasetid": "document", "objectid": 122155, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "32c939d232c02ea77323982c6d2a00a1", "hash_type": "MD5", "filesize": 1303, "mtime": "2021-06-23 21:49:01", "url": "/2129/6/indexcodes.txt" } ], "eprint_id": 2129, "pos": 6, "placement": 6, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from text/plain to indexcodes", "language": "en", "security": "internal", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/10671" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/10671" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/10671" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/21/29", "datestamp": "2004-05-27", "lastmod": "2022-01-15 00:21:38", "status_changed": "2009-09-25 02:27:40", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Aoki-Ichiro", "name": { "family": "Aoki", "given": "Ichiro" }, "show_email": "NO" } ] }, "title": "Distributed Active Transformer for Integrated Power Amplification", "ispublished": "unpub", "full_text_status": "public", "keywords": "(Electrical Engineering)", "abstract": "A novel on-chip impedance transformation and power-combining technique, the distributed active transformer (DAT) is introduced. It overcomes the fundamental difficulties presented by silicon technology in the design of integrated rf power amplifiers. This technique efficiently combines several low-voltage push-pull amplifiers and simultaneously performs an impedance transformation to produce a larger output power while maintaining a 50\u03a9 match. It also uses virtual ac grounds and magnetic couplings extensively to eliminate the need for any off-chip component, such as tuned bonding wires or external inductors. Furthermore, it desensitizes the operation of the amplifier to the inductance of bonding wires making the design more repeatable.
\r\n\r\nIn this work, the performance of the introduced DAT structure is compared to that of conventional on-chip impedance transformation methods. Their fundamental power-efficiency limitations in the design of high-power fully-integrated amplifiers in standard silicon process technologies are analyzed and the DAT is demonstrated to be more efficient. Furthermore, different classes of power amplification operations and their use in DAT power amplifiers are studied.
\r\n\r\nTo demonstrate the feasibility of this concept several silicon integrated power amplifiers have been fabricated and measured including a 2.4-GHz, 2-W, 2-V truly fully-integrated power amplifier with 50\u03a9 on-chip input and output matching using 0.35\u00b5m CMOS transistors. It achieves a power added efficiency (PAE) of 41 % at this power level, demonstrating for the first time a truly fully-integrated watt-level GHz range CMOS power amplifier. It can also produce 450mW using a 1 V supply. A two stage DAT prototype, also at 2.4GHz using the same technology, operates with higher gain and lower supply voltage achieving 1-W output power, 30% PAE, and 14-dB gain with 1.15-V supply.
", "date": "2002", "date_type": "degree", "id_number": "CaltechETD:etd-05272004-094928", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05272004-094928", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2004-05-27", "doi": "10.7907/6XMD-MR86", "divisions": { "items": [ "div_eng" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Rutledge-D-B", "name": { "family": "Rutledge", "given": "David B." }, "role": "chair" }, { "id": "Hajimiri-A", "name": { "family": "Hajimiri", "given": "Ali" }, "orcid": "0000-0001-6736-8019", "role": "member" }, { "id": "Bruck-J", "name": { "family": "Bruck", "given": "Jehoshua" }, "orcid": "0000-0001-8474-0812", "role": "member" }, { "id": "Weinreb-S", "name": { "family": "Weinreb", "given": "Sander" }, "orcid": "0000-0002-9353-6204", "role": "member" }, { "id": "Tai-Yu-Chong", "name": { "family": "Tai", "given": "Yu-Chong" }, "orcid": "0000-0001-8529-106X", "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2004-05-27", "thesis_defense_date": "2001-10-31", "thesis_approved_date": "2004-05-27", "review_status": "approved", "option_major": { "items": [ "eleceng" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2002", "author_list": "Aoki, Ichiro", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Rutledge, David B.; Hajimiri, Ali; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/1979", "eprint_id": 1979, "rev_number": 16, "documents": [ { "id": "/id/document/3465", "doc_id": 3465, "rev_number": 3, "files": [ { "id": "/id/file/20520", "fileid": 20520, "datasetid": "document", "objectid": 3465, "filename": "Szczepankiewicz_sh_2001.pdf", "mime_type": "application/pdf", "filesize": 6977318, "mtime": "2012-12-26 02:45:03", "url": "/1979/1/Szczepankiewicz_sh_2001.pdf" } ], "eprint_id": 1979, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Szczepankiewicz_sh_2001.pdf", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "final", "relation": { "items": [ { "type": "http://eprints.org/relation/hasVolatileVersion", "uri": "/id/document/20140" }, { "type": "http://eprints.org/relation/haspreviewThumbnailVersion", "uri": "/id/document/20140" }, { "type": "http://eprints.org/relation/hasVersion", "uri": "/id/document/20140" } ] } }, { "id": "/id/document/16551", "doc_id": 16551, "rev_number": 3, "files": [ { "id": "/id/file/202230", "fileid": 202230, "datasetid": "document", "objectid": 16551, "filename": "Szczepankiewicz__Steven_Henry_2001.txt", "mime_type": "text/plain", "filesize": 1540, "mtime": "2016-08-22 21:15:22", "url": "/1979/2/Szczepankiewicz__Steven_Henry_2001.txt" } ], "eprint_id": 1979, "pos": 2, "format": "text/plain", "language": "en", "security": "internal", "license": "other", "main": "Szczepankiewicz__Steven_Henry_2001.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "content": "release" }, { "id": "/id/document/20140", "doc_id": 20140, "rev_number": 2, "files": [ { "id": "/id/file/20518", "fileid": 20518, "datasetid": "document", "objectid": 20140, "filename": "preview.png", "mime_type": "image/png", "hash": "5158aeef6c94a5fce50d1ded5424c9b8", "hash_type": "MD5", "filesize": 9223, "mtime": "2012-12-26 02:45:03", "url": "/1979/3/preview.png" } ], "eprint_id": 1979, "pos": 3, "placement": 3, "mime_type": "image/png", "format": "image/png", "language": "en", "security": "public", "license": "other", "main": "preview.png", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/3465" }, { "type": "http://eprints.org/relation/ispreviewThumbnailVersionOf", "uri": "/id/document/3465" }, { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/3465" } ] } }, { "id": "/id/document/121742", "doc_id": 121742, "rev_number": 1, "files": [ { "id": "/id/file/367134", "fileid": 367134, "datasetid": "document", "objectid": 121742, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "40df5bfa135c5e87d03131adf9b24070", "hash_type": "MD5", "filesize": 753, "mtime": "2021-06-23 21:34:15", "url": "/1979/4/indexcodes.txt" } ], "eprint_id": 1979, "pos": 4, "placement": 4, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from text/plain to indexcodes", "language": "en", "security": "internal", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/16551" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/16551" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/16551" } ] } } ], "eprint_status": "archive", "userid": 2, "dir": "disk0/00/00/19/79", "datestamp": "2006-05-23", "lastmod": "2022-11-29 23:42:55", "status_changed": "2009-09-25 02:21:57", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "szczepas@canisius.edu", "id": "Szczepankiewicz-Steven-Henry", "name": { "family": "Szczepankiewicz", "given": "Steven Henry" }, "show_email": "NO" } ] }, "title": "Surface Chemistry of TiO\u2082 Photocatalysts", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The surface chemistry of TiO\u2082 photocatalysts have been characterized by infrared spectroscopy, alcalimetric titrations, and photocatalytic reactivity. The fundamental processes governing electron transfer at the surface were investigated by inhibiting the photocatalytic reactions.
\r\n\r\nFree and trapped charge carriers in polycrystalline TiO\u2082 following bandgap irradiation are characterized by diffuse reflectance IR spectroscopy (DRIFTS). Irradiation of anatase in vacuo or in the presence of CD\u2083OD leads to decreased overall reflectance, to an absorbance at 3717 cm\u207b\u00b9, and to the decline of a 3647 cm\u207b\u00b9 band. x persists for days in vacuum or dry O\u2082 and is only bleached by the action of [O\u2082 + H\u2082O(g) + hv]. It is assigned to a Ti(III)O-H vibration ensuing electron trapping at the acidic Ti(IV)OH centers that absorb at 3647 cm\u207b\u00b9. Irradiation under O\u2082 yields a band at 3683 cm\u207b\u00b9 (Y) that corresponds to bound OH radicals. These last indefinitely in vacuo, but decay in a few hours under O\u2082. Since none of the above phenomena occur on defective TiO\u2082-x, materials obtained by thermal annealing under vacuum, photochemical damage to actual catalysts involves concurrent surface reorganization. The presence of the 3717 cm\u207b\u00b9 band is used to confirm this reorganization.
\r\n\r\nThe decreased reflectivity is due to a spectrum-wide absorption signal proportional to \u03bb1.7 (\u03bb = wavelength/\u00b5m), which indicates the presence of free conduction band electrons coupled with acoustic phonons in the lattice. Free electrons appear to decay according to saturation kinetics. The fitted parameters indicate a limited number of reversible trapping states. The concentration of these states appears to be diminished by sequential UV treatments. A broad IR absorption peak centered at 3380 cm\u207b\u00b9 is attributed to an electronic transition from an occupied surface electron trap 0.42 eV below the conduction band. The free carrier decay lifetime is lengthened as the samples are dehydrated.
\r\n\r\nElectric fields generated by photoexcited charge carriers in TiO\u2082 (anatase) produce Stark effect intensity and wavelength shifts for surface TiO-H stretching vibrations. Shallow electron-trapping states, observed as broad absorption bands above 3000 cm\u207b\u00b9, produce an apparently homogeneous electric field. Intensity changes and corresponding wavelength shifts for v(TiO-H) are proportional to the magnitude and polarity of the electric field. O\u2082 is shown to reversibly abstract electrons from shallow trapping states. These results suggest that shallow electron traps are not associated with localized structures, but rather are delocalized across the TiO\u2082 surface.
\r\n\r\nThe effect of poisoning the photocatayst is monitored during the oxidation of a phosphorous-containing organic substrate. The photoassisted oxidation of dimethyl-methyl-phosphonate (DMMP) over UV-irradiated TiO\u2082 is investigated as a simulant for warfare nerve agent detoxification. Adsorption uptake measurements are performed by MS analysis of a fine DMMP aerosol up and downstream of an adsorbant TiO\u2082 film. Photodesorption processes, gas phase intermediates and mineral products are quantified in situ by headspace GC-MS analysis of a static system. Non-volatile intermediates and products are analyzed by HPLC analysis of both aqueous and organic extractions from the Ti02 film. Adsorbed intermediates are characterized and quantified in situ by DRIFTS of TiO\u2082 powders. Specific site binding of DMMIP and catalyst poisoning are observed in the DRIFT spectra. A proposed mechanism suggests rapid detoxification of DMMP as a simulant, but extensive poisoning of the catalyst by the end products.
\r\n\r\nIn a comparative investigation of titania surface chemistry, TiO\u2082 Q particles are synthesized and characterized by transmission electron microscopy, potentiometric titration, infrared analysis, and photocatalytic reactivity. TEM images show small individual particulates of anatase about 2 nm in diameter. Potentiometric titrations confirm the presence of a highly protonated gel layer on the surface of these particles. The infrared spectra indicate that this layer is amorphous. An autocatalytic enhancement of the photocatalysts during photooxidation of methyl orange suggests that reaction intermediates cause the collapse of the hydrated gel layer into a more active surface.
\r\n\r\nTwo supplementary investigations are presented which confirm the previous results. MAS NMR data is presented which shows a paramagnetic influence from surface trapped electrons. The data also suggests localized trapping at a characteristic type of TiOH surface moiety. Theoretical calculations also confirm the band assignments presented in the previous chapters by reproducing the data with the predicted structural assignments.
", "date": "2001", "date_type": "degree", "id_number": "CaltechETD:etd-05232006-094537", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechETD:etd-05232006-094537", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_by": "Imported from ETD-db", "deposited_on": "2006-05-23", "doi": "10.7907/HABJ-3T48", "alt_title": { "items": [ "Surface chemistry of titanium dioxide photocatalysts" ] }, "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "McKoy-B-V", "name": { "family": "McKoy", "given": "Basil Vincent" }, "role": "chair" }, { "id": "Hoffmann-M-R", "name": { "family": "Hoffmann", "given": "Michael R." }, "orcid": "0000-0001-6495-1946", "role": "member" }, { "id": "Lewis-N-S", "name": { "family": "Lewis", "given": "Nathan Saul" }, "orcid": "0000-0001-5245-0538", "role": "member" }, { "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716", "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_submitted_date": "2006-05-23", "thesis_defense_date": "2001-03-12", "thesis_approved_date": "2006-05-23", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive\nlicense to archive and make accessible, under the conditions specified below,\nmy thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "2001", "author_list": "Szczepankiewicz, Steven Henry", "advisor_list": "Janda, Kenneth C.", "comittee_list": "McKoy, Basil Vincent; Hoffmann, Michael R.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/8219", "eprint_id": 8219, "rev_number": 35, "documents": [ { "id": "/id/document/47575", "doc_id": 47575, "rev_number": 3, "files": [ { "id": "/id/file/139109", "fileid": 139109, "datasetid": "document", "objectid": 47575, "filename": "Maron_j_2001.pdf", "mime_type": "application/pdf", "hash": "78287ed9fa7b82a2820292363f4bfdb3", "hash_type": "MD5", "filesize": 13543876, "mtime": "2014-05-05 22:26:09", "url": "/8219/1/Maron_j_2001.pdf" } ], "eprint_id": 8219, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"/id/document/47575" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/47575" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/82/19", "datestamp": "2014-05-06 14:42:48", "lastmod": "2022-09-12 22:50:54", "status_changed": "2014-05-06 14:42:48", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Maron-Jason-L", "name": { "family": "Maron", "given": "Jason L." }, "show_email": "NO" } ] }, "title": "Magnetohydrodynamic Turbulence", "ispublished": "unpub", "full_text_status": "public", "keywords": "(Physics)", "abstract": "We simulate incompressible, MHD turbulence using a pseudo-spectral code. Our\r\nmajor conclusions are as follows.
\r\n\r\n1) MHD turbulence is most conveniently described in terms of counter propagating\r\nshear Alfv\u00e9n and slow waves. Shear Alfv\u00e9n waves control the cascade dynamics. Slow\r\nwaves play a passive role and adopt the spectrum set by the shear Alfv\u00e9n waves. Cascades\r\ncomposed entirely of shear Alfv\u00e9n waves do not generate a significant measure\r\nof slow waves.
\r\n\r\n2) MHD turbulence is anisotropic with energy cascading more rapidly along k\u22a5 than\r\nalong k\u2225, where k\u22a5 and k\u2225 refer to wavevector components perpendicular and parallel\r\nto the local magnetic field. Anisotropy increases with increasing k\u22a5 such that excited\r\nmodes are confined inside a cone bounded by k\u2225 \u221d k\u03b3\u22a5 where \u03b3 less than 1. The opening\r\nangle of the cone, \u03b8(k\u22a5) \u221d k-(1-\u03b3)\u22a5, defines the scale dependent anisotropy.
\r\n\r\n3) MHD turbulence is generically strong in the sense that the waves which comprise it\r\nsuffer order unity distortions on timescales comparable to their periods. Nevertheless,\r\nturbulent fluctuations are small deep inside the inertial range. Their energy density is less than that of the background field by a factor \u03b82 (k\u22a5)\u226a1.
\r\n\r\n4) MHD cascades are best understood geometrically. Wave packets suffer distortions\r\nas they move along magnetic field lines perturbed by counter propagating waves.\r\nField lines perturbed by unidirectional waves map planes perpendicular to the local\r\nfield into each other. Shear Alfv\u00e9n waves are responsible for the mapping's shear and\r\nslow waves for its dilatation. The amplitude of the former exceeds that of the latter\r\nby 1/\u03b8(k\u22a5) which accounts for dominance of the shear Alfv\u00e9n waves in controlling\r\nthe cascade dynamics.
\r\n\r\n5) Passive scalars mixed by MHD turbulence adopt the same power spectrum as the\r\nvelocity and magnetic field perturbations.
\r\n\r\n6) Decaying MHD turbulence is unstable to an increase of the imbalance between\r\nthe flux of waves propagating in opposite directions along the magnetic field. Forced\r\nMHD turbulence displays order unity fluctuations with respect to the balanced state\r\nif excited at low k by \u03b4(t) correlated forcing. It appears to be statistically stable to\r\nthe unlimited growth of imbalance.
\r\n\r\n7) Gradients of the dynamic variables are focused into sheets aligned with the magnetic\r\nfield whose thickness is comparable to the dissipation scale. Sheets formed by\r\noppositely directed waves are uncorrelated. We suspect that these are vortex sheets\r\nwhich the mean magnetic field prevents from rolling up.
\r\n\r\n8) Items (1)-(5) lend support to the model of strong MHD turbulence put forth by\r\nGoldreich and Sridhar (1995, 1997). Results from our simulations are also consistent\r\nwith the GS prediction \u03b3 = 2/3. The sole not able discrepancy is that the 1D power\r\nlaw spectra, E(k\u22a5) \u221d k-\u221d\u22a5, determined from our simulations exhibit \u221d \u2248 3/2, whereas\r\nthe GS model predicts \u221d = 5/3.
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W." }, "role": "co-chair" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "2000-09-19", "review_status": "approved", "option_major": { "items": [ "physics" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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"type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/34809" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/74/15", "datestamp": "2013-01-22 17:39:41", "lastmod": "2021-11-05 20:04:43", "status_changed": "2013-01-22 17:39:41", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Evard-Dwight-David", "name": { "family": "Evard", "given": "Dwight David" }, "show_email": "NO" } ] }, "title": "Structure and Dynamics of Several Rare Gas-Halogen van der Waals Molecules", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The structure and dynamics of several rare gas-halogen van der Waals molecules have been studied in the six laser-free jet expansion experiments which are described in this thesis. High resolution (0.01 cm\u207b\u00b9 spectra were obtained for one B \u2190 X transition of both NeBr\u2082 and NeCl\u2082, in order to determine the structure and lifetime of these complexes in the ground and excited states. NeCl\u2082 was studied extensively at moderate resolution (0.05 cm\u207b\u00b9 to probe the potential energy surface and the correlation of the van der Waals bond with the covalent bond. The lifetime of metastable vibrationally excited NeBr\u2082 X(\u03bd = 1) was determined directly by measuring its concentration as a function of distance from the source to the detection region. A pump-probe technique was used to study ArCl\u2082 to probe the structure and dynamics of the complex. Ar\u2099Cl\u2082 (n = 1, 2, 3) was studied to test the validity of the bond-bond additivity model of binding for the complex. This set of experiments has provided a great deal of information on the nature of the structure and dynamics of the complexes.
", "date": "1988", "date_type": "degree", "id_number": "CaltechTHESIS:01222013-092417239", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01222013-092417239", "related_url": { "items": [ { "description": "Article adapted for Chapter II.", "type": "doi", "url": "https://doi.org/10.1063/1.448610" }, { "description": "Article adapted for Chapter III.", "type": "doi", "url": "https://doi.org/10.1063/1.450200" }, { "description": "Article adapted for Chapter IV.", "type": "doi", "url": "https://doi.org/10.1021/j100294a014" }, { "description": "Article adapted for Chapter V.", "type": "doi", "url": "https://doi.org/10.1016/0009-2614(87)80223-3" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-01-22 17:39:41", "doi": "10.7907/90wr-zj81", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "chair" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1987-09-21", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/34801" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/34801" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/74/12", "datestamp": "2013-01-22 17:30:00", "lastmod": "2021-11-05 20:04:32", "status_changed": "2013-01-22 17:30:00", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Cline-Joseph-Isaac-III", "name": { "family": "Cline", "given": "Joseph Isaac, III" }, "show_email": "NO" } ] }, "title": "Photodissociation Dynamics of Triatomic van der Waals Molecules", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemsitry", "abstract": "The spectroscopy and vibrational predissociation dynamics of triatomic van der Waals molecules are studied experimentally and theoretically at the state-to-state level of detail.
\r\n\r\nLaser-induced fluorescence spectra of HeCl2 are measured and the geometry and vibrational predissociation rate are obtained by a rotational analysis of the spectra and the determination of homogenous linewidths. A laser pump-probe technique is used to measure the vibrational and rotational state population distribution of the product Cl2. Although the Cl2 fragment has little rotational energy, its rotational distribution is bimodal. A symmetry selection rule for the dissociation results from the symmetry of the He \u2022 \u2022 \u2022 Cl2 van der Waals potential. Quantum mechanical calculations on a realistic potential energy surface are successful in modeling the experimental spectroscopy and dynamics.
\r\n\r\nThe vibrational predissociation dynamics of NeCl2 is also measured using the pump-probe technique. In this case the Cl2 fragment shows significantly more rotational excitation than in the dissociation of HeCl2. The rotational distributions are bimodal and are relatively independent of the energy of the prepared state. The NeCl2 binding energy is estimated from thresholds for the populations of fragment rotational levels.
\r\n\r\nThe vibrational predissociation of NeBr2 is studied by dispersing the fluorescence of the Br2 fragment. The product Br2 is rotationally cold. The closure of vibrational product channels is used to determine the binding energy of the molecule.
", "date": "1988", "date_type": "degree", "id_number": "CaltechTHESIS:01182013-155753371", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01182013-155753371", "related_url": { "items": [ { "description": "Article adapted for Chapter 2.", "type": "doi", "url": "https://doi.org/10.1063/1.450507" }, { "description": "Article adapted for Chapter 3.", "type": "doi", "url": "https://doi.org/10.1103/physreva.36.1944" }, { "description": "Article adapted for Chapter 4.", "type": "doi", "url": "https://doi.org/10.1063/1.452204" }, { "description": "Book chapter adapted for Chapter 5.", "type": "doi", "url": "https://doi.org/10.1007/978-94-009-3969-1_39" } ] }, "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2013-01-22 17:30:00", "doi": "10.7907/f38f-hb60", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Kuppermann-A", "name": { "family": "Kuppermann", "given": "Aron" }, "role": "chair" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "orcid": "0000-0003-1464-2461", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1988-01-18", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1988", "author_list": "Cline, Joseph Isaac, III", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Kuppermann, Aron; Janda, Kenneth C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/7413", "eprint_id": 7413, "rev_number": 27, "documents": [ { "id": "/id/document/34769", "doc_id": 34769, "rev_number": 3, "files": [ { "id": "/id/file/110176", "fileid": 110176, "datasetid": "document", "objectid": 34769, "filename": "Hair_sr_1988.pdf", "mime_type": "application/pdf", "hash": "74e954ea88d82080dfe7a49eb0d816ea", "hash_type": "MD5", "filesize": 22905638, "mtime": "2013-01-19 00:08:13", "url": "/7413/1/Hair_sr_1988.pdf" } ], "eprint_id": 7413, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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"http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/34769" } ] } } ], "eprint_status": "archive", "userid": 87, "dir": "disk0/00/00/74/13", "datestamp": "2013-01-22 16:21:09", "lastmod": "2021-11-05 20:05:06", "status_changed": "2013-01-22 16:21:09", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Hair-Sally-Reid", "name": { "family": "Hair", "given": "Sally Reid" }, "show_email": "NO" } ] }, "title": "Experimental and Theoretical Studies of van der Waals Molecule Photodissociation", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "Three studies are reported on the vibrational predissociation of polyatomic van der Waals complexes. In the first, the ethylene dimer and rare gas-ethylene complexes are treated theoretically, using a local mode quantum mechanical technique. The ethylene dimer exhibits extensive mixing between the initially excited \u03bd\u2087 vibration and nearby combinations of the \u03bd\u2081\u2080 and van der Waals vibrations, while the rare gas- ethylene complexes do not. Mixing is extensive enough in the ethylene dimer to spread the oscillator strength of the \u03bd\u2087 vibration over a 10 cm\u207b\u00b9 region of the spectrum, in agreement with the experimentally observed band.
\r\n\r\nThe second study is a low resolution photodissociation experiment on the ethylene-methane complex. The spectra observed by exciting the \u03bd\u2087 ethylene vibration of C\u2082H\u2084-CH\u2084, C\u2082H\u2084-CH\u2082D\u2082, and C\u2082H\u2084-CD\u2084 all exhibit the same width. This indicates that the shapes and widths of the observed spectra are not determined by unresolved or power-broadened rotational structure. This result underscores the importance of vibrational coupling in the dissociation process.
\r\n\r\nThe final study is a laser pump-probe experiment on the Ne\u2082Cl\u2082 and Ne\u2083Cl\u2082 complexes. The Ne\u2082Cl\u2082 complex has a distorted tetrahedral geometry, as determined from high resolution, excitation spectra. Excitation shift arguments suggest a structure for Ne\u2083Cl\u2082 with the three neon atoms encircling the Cl\u2082 bond axis. The total van der Waals bond energy of the Ne\u2082Cl\u2082 complex is found to be between 145.6 and 148.6 cm\u207b\u00b9. When energetically possible, the Ne\u2082Cl\u2082 complex can dissociate by losing a single quantum of Cl\u2082 stretching energy. This indicates that the two neon atoms do not dissociate by two independent \"half-collisions.\" The Cl\u2082 fragment rotational excitation is found to depend only weakly on the energy available to the fragments.
\r\n\r\n\r\n", "date": "1988", "date_type": "degree", "id_number": "CaltechTHESIS:01182013-160624319", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:01182013-160624319", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_by": "Benjamin Perez", "deposited_on": "2013-01-22 16:21:09", "doi": "10.7907/anb1-sr68", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Kuppermann-A", "name": { "family": "Kuppermann", "given": "Aron" }, "role": "chair" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "email": "dadougherty@caltech.edu", "id": "Dougherty-D-A", "name": { "family": "Dougherty", "given": "Dennis A." }, "orcid": "0000-0003-1464-2461", "role": "member" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1988-05-03", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1988", "author_list": "Hair, Sally Reid", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Kuppermann, Aron; Janda, Kenneth C.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11381", "eprint_id": 11381, "rev_number": 24, "documents": [ { "id": "/id/document/96621", "doc_id": 96621, "rev_number": 4, "files": [ { "id": "/id/file/276742", "fileid": 276742, "datasetid": "document", "objectid": 96621, "filename": "Hanratty_MA_1985.pdf", "mime_type": "application/pdf", "hash": "dab41082555ac3f21bdc717f8d63f5f7", "hash_type": "MD5", "filesize": 62055541, "mtime": "2019-02-01 20:09:55", "url": "/11381/1/Hanratty_MA_1985.pdf" } ], "eprint_id": 11381, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", 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These investigations are discussed in Chapter II. Infrared activation effected with a cw CO2 laser is highly selective, with dissociation occurring only by the lowest energy pathway.
\r\n\r\nChapter III describes the use of product translational energy release distributions to investigate the potential energy surfaces for elimination of H2 and small hydrocarbons from ionic cobalt and nickel complexes with alkanes. The measurements were made using a reverse geometry double focusing mass spectrometer. For dehydrogenation reactions, both the shape of the kinetic energy release distribution and the maximum kinetic energy release appear to be correlated with the reaction mechanism. Statistical RRKM theory is used to model the observed kinetic energy release distributions.
\r\n\r\nThe kinetic energy release distributions associated with loss of H2 and small hydrocarbons from Co(C5H10)+ complexes are presented in Chapter IV. The results from the ionic cobalt-alkene adducts are compared with the kinetic energy release distributions for the ionic cobalt-alkane complexes discussed in Chapter III. Collision induced dissociation is also employed to characterize the Co(C5H10)+ adducts.
\r\n\r\nThe formation and reactions of iron and nickel clusters containing up to four metal atoms with a varying number of CO ligands are discussed in Chapter V. Ion-molecule condensation reactions result in the rapid formation of polynuclear metal carbonyl clusters which lose CO when exposed to infrared or visible radiation. The reactivity of these ligated species is markedly different from that of the bare metal ion. The potential of this method for generating very specific unsaturated cluster compounds is demonstrated.
\r\n\r\n", "date": "1985", "date_type": "degree", "id_number": "CaltechTHESIS:02012019-115455977", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:02012019-115455977", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Atlantic Richfield Corporation" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_on": "2019-02-01 20:52:28", "doi": "10.7907/6mqm-3w23", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "chair" }, { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "member" }, { "email": "wag@caltech.edu", "id": "Goddard-W-A-III", "name": { "family": "Goddard", "given": "William A., III" }, "orcid": "0000-0003-0097-5716", "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "orcid": "0000-0002-0057-7817", "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1985-04-09", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1985", "author_list": "Hanratty, Maureen Alice", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Janda, Kenneth C.; Beauchamp, Jesse L.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11218", "eprint_id": 11218, "rev_number": 17, "documents": [ { "id": "/id/document/94469", "doc_id": 94469, "rev_number": 4, "files": [ { "id": "/id/file/267063", "fileid": 267063, "datasetid": "document", "objectid": 94469, "filename": "Schultz_JC_1984.pdf", "mime_type": "application/pdf", "hash": "fa0155261be5d130ab29186287163504", "hash_type": "MD5", "filesize": 47134370, "mtime": "2018-10-03 16:29:43", "url": "/11218/1/Schultz_JC_1984.pdf" } ], "eprint_id": 11218, "pos": 1, "placement": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": 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"http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/94469" } ] } } ], "eprint_status": "archive", "userid": 11566, "dir": "disk0/00/01/12/18", "datestamp": "2018-10-04 18:56:28", "lastmod": "2021-11-05 20:03:11", "status_changed": "2018-10-04 18:56:28", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Schultz-Jocelyn-Chupka", "name": { "family": "Schultz", "given": "Jocelyn Chupka" }, "show_email": "NO" } ] }, "title": "Photoelectron Spectroscopy of Alkyl and Alkenyl Free Radicals", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry", "abstract": "The first bands of the photoelectron spectra of simple alkyl and alkenyl free radicals, produced by pyrolysis of organic nitrites, are presented. Thermochemical and structural information about the corresponding carbocations in the gas phase are obtained from interpreting the spectra. In particular, adiabatic ionization potentials are combined with radical heats of formation to obtain heats of formation of the cations. The photoelectron band shapes are discussed in terms of structural changes occurring upon ionization. The focus of this work is\u00b7 the study of isomeric radicals. Their photoelectron spectra allow the characterization of a series of carbocations with well-defined structures, namely those which closely resemble the radicals, even when the cations can rearrange with little or no activation energy to more stable forms. Radical thermal rearrangement and decomposition pathways are also studied.
\r\n\r\nChapter I provides a brief introduction to the field of photoelectron spectroscopy of transient species, including a compilation of photoelectron data of transient species, and an introduction to the specific work presented in this thesis. Chapter II presents the photoelectron spectra of the C4H7 radicals 1-methylallyl, 2-methylallyl, allylcarbinyl and cyclobutyl radical, which provide information about the corresponding C4H+7 carbocations in the gas phase. These cations are of longstanding interest in the cyclopropylcarbinyl, cyclobutyl and allylcarbinyl interconversions observed in solvolysis reactions. The photoelectron spectra of 1-propyl, 1-butyl, isobutyl, neopentyl and 2-butyl radicals are presented in Chapter III. The corresponding primary cations are of particular interest because they are often postulated as intermediates or transition states in gas-phase and solution isomerization processes.
\r\n\r\nChapter IV describes the application of photoelectron spectroscopy to the study of low-pressure gas-surface reactions. Organic radicals, as well as stable products, have been detected directly after exiting the catalyst bed. Allylic hydrogen abstraction by heated bismuth oxide catalyst forms gas-phase allyl and 2-methylallyl radicals from propylene and isobutylene in the presence of oxygen. Mechanistic information is obtained by varying the catalyst temperature and reactant partial pressures.
\r\n", "date": "1984", "date_type": "degree", "id_number": "CaltechTHESIS:10032018-091338203", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10032018-091338203", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "collection": "CaltechTHESIS", "reviewer": "Kathy Johnson", "deposited_on": "2018-10-04 18:56:28", "doi": "10.7907/r2r1-k971", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "jlbchamp@caltech.edu", "id": "Beauchamp-J-L", "name": { "family": "Beauchamp", "given": "Jesse L." }, "orcid": "0000-0001-8839-4822", "role": "chair" }, { "id": "Roberts-J-D", "name": { "family": "Roberts", "given": "John D." }, "role": "member" }, { "id": "Sparks-Randal-K", "name": { "family": "Sparks", "given": "Randal K." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1983-08-19", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1984", "author_list": "Schultz, Jocelyn Chupka", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Beauchamp, Jesse L.; Roberts, John D.; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/11838", "eprint_id": 11838, "rev_number": 18, "documents": [ { "id": "/id/document/103616", "doc_id": 103616, "rev_number": 3, "files": [ { "id": "/id/file/309057", "fileid": 309057, "datasetid": "document", "objectid": 103616, "filename": "Moll_DJ_1983.zip", "mime_type": "application/x-zip", "hash": "058d2e539a1f903f16c99d404ecac4a8", "hash_type": "MD5", "filesize": 251065274, "mtime": "2019-10-22 00:51:02", "url": "/11838/1/Moll_DJ_1983.zip" } ], "eprint_id": 11838, "pos": 1, "placement": 1, "mime_type": "application/x-zip", "format": "application/zip", "format_desc": "TIFFs", "language": "en", 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"http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/103617" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/103617" } ] } } ], "eprint_status": "archive", "userid": 8820, "dir": "disk0/00/01/18/38", "datestamp": "2019-10-22 18:08:53", "lastmod": "2021-11-05 20:03:49", "status_changed": "2019-10-22 18:08:53", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "id": "Moll-David-Jerry", "name": { "family": "Moll", "given": "David Jerry" }, "show_email": "NO" } ] }, "title": "One- and Two-Color Laser Spectroscopy with Photoacoustic and Multiphoton Ionization Detection", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry; Applied Physics", "abstract": "The techniques of pulsed photoacoustic spectroscopy and multiphoton ionization spectroscopy have been used to study several types of weak optical transitions in the ultraviolet or visible spectral regions for gas phase molecules. Both one- and two-color experiments have been performed. The one-color experiments involved the study of high vibrational overtones and spin-forbidden transitions. The two-color experiments demonstrated the application of photoacoustic detection of stimulated emission pumping for populating high vibration levels of the ground electronic state. Two-color experiments were also used to study excited state absorption processes in aniline.
\r\n\r\nPulsed laser photoacoustic spectra of CD3H in the region of the \u2207vCH = 5, 6, and 7 CH stretch overtones were obtained. These overtones and nearby combination bands displayed sharp rotational structure, indicating a minimum excited state population relaxation time of 5 x 10-12 sec. A combination sum analysis was used to generate excited state rotational constants B'. These constants reflect the geometries of the excited states, and therefore provide a sensitive probe of the mixing between various zero order excited states.
\r\n\r\nPhotoacoustic detection was used to monitor a stimulated emission pumping process in p-difluorobenzene. Using the Ã1B2u 5' state as an intermediate state, several vibrational levels of the ground electronic state were populated. The photoacoustic technique is an attractive alternative to other techniques because of its sensitivity, simplicity, and its ability to differentiate between stimulated emission pumping and excited state absorption.
\r\n\r\nTime-resolved excited state absorption studies were performed on aniline using the multiphoton ionization and photoacoustic detection techniques. Signals from both of these techniques were measured as a function of the time delay between two laser pulses of different wavelength. The first pulse excited the S1 0-0 transition. The second pulse excited either S1 or a triplet state produced by intersystem crossing, depending on the time delay between pulses. Both ionization and dissociation processes were observed. By varying the conditions of excitation, it appears that a given amount of energy can be selectively channeled into either ionization or dissociation pathways. These results were explained using a simple Franck Condon factor model.
\r\n\r\nThe application of pulsed laser photoacoustic spectroscopy to the study of weak absorptions in the visible and ultraviolet spectral regions was investigated. Photoacoustic spectra of triplet states in CS2, SO2, biacetyl, and thiophosgene were obtained. An attempt to detect the ã3B1u state in benzene, produced instead a two-photon spectrum of several Rydberg states. It was discovered that the sensitivity of the pulsed photoacoustic technique for extremely weak absorptions is limited by the increased probability of multiphoton absorption when high intensities are used.
\r\n\r\nFinally, in two appendices, the detection of the ã3A2 state in CS2 by the multiphoton ionization technique is presented. The CS2 study demonstrates the utility of the multiphoton ionization technique for detecting spin-forbidden transitions at high resulution and with great sensitivity.
", "date": "1983", "date_type": "degree", "id_number": "CaltechTHESIS:10212019-175021360", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:10212019-175021360", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "Department of Energy (DOE)", "grant_number": "DE-AS03-765F00767" }, { "agency": "Eastman Kodak Company" }, { "agency": "Shell Companies Foundation" }, { "agency": "Caltech" } ] }, "collection": "CaltechTHESIS", "reviewer": "Melissa Ray", "deposited_by": "Mel Ray", "deposited_on": "2019-10-22 18:08:53", "doi": "10.7907/60wm-py84", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "id": "Kuppermann-A", "name": { "family": "Kuppermann", "given": "Aron" }, "role": "chair" }, { "email": "mckoy@caltech.edu", "id": "McKoy-B-V", "name": { "family": "McKoy", "given": "Basil Vincent" }, "role": "member" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1983-02-16", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "option_minor": { "items": [ "appliedphys" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1983", "author_list": "Moll, David Jerry", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Kuppermann, Aron; McKoy, Basil Vincent; et el." }, { "id": "https://thesis.library.caltech.edu/id/eprint/6860", "eprint_id": 6860, "rev_number": 41, "documents": [ { "id": "/id/document/14431", "doc_id": 14431, "rev_number": 5, "files": [ { "id": "/id/file/92604", "fileid": 92604, "datasetid": "document", "objectid": 14431, "filename": "Mayer_jm_1983.pdf", "mime_type": "application/pdf", "filesize": 114675845, "mtime": "2012-12-26 04:40:59", "url": "/6860/1/Mayer_jm_1983.pdf" } ], "eprint_id": 6860, "pos": 1, "mime_type": "application/pdf", "format": "application/pdf", "language": "en", "security": "public", "license": "other", "main": "Mayer_jm_1983.pdf", "media_duration": "0", "media_aspect_ratio": "0", 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127274, "rev_number": 1, "files": [ { "id": "/id/file/372708", "fileid": 372708, "datasetid": "document", "objectid": 127274, "filename": "indexcodes.txt", "mime_type": "text/plain", "hash": "e7f3cd10f299f63666f7ab7bf4cfb7b6", "hash_type": "MD5", "filesize": 69, "mtime": "2021-06-24 01:36:35", "url": "/6860/7/indexcodes.txt" } ], "eprint_id": 6860, "pos": 7, "placement": 7, "mime_type": "text/plain", "format": "other", "format_desc": "Generate index codes conversion from application/pdf to indexcodes", "language": "en", "security": "internal", "license": "other", "main": "indexcodes.txt", "media_duration": "0", "media_aspect_ratio": "0", "media_sample_start": "0", "media_sample_stop": "0", "relation": { "items": [ { "type": "http://eprints.org/relation/isVersionOf", "uri": "/id/document/14433" }, { "type": "http://eprints.org/relation/isVolatileVersionOf", "uri": "/id/document/14433" }, { "type": "http://eprints.org/relation/isIndexCodesVersionOf", "uri": "/id/document/14433" } ] } } ], "eprint_status": "archive", "userid": 50, "dir": "disk0/00/00/68/60", "datestamp": "2012-03-21 22:08:12", "lastmod": "2022-11-09 19:20:07", "status_changed": "2012-03-21 22:08:11", "type": "thesis", "metadata_visibility": "show", "creators": { "items": [ { "email": "mayer@chem.washington.edu", "id": "Mayer-James-Moers", "name": { "family": "Mayer", "given": "James Moers" }, "orcid": "0000-0002-3943-5250", "show_email": "NO" } ] }, "title": "Synthesis, Characterization, and Reactivity of New Hydride Compounds of Tantalum (V)", "ispublished": "unpub", "full_text_status": "public", "keywords": "Chemistry, tantalum, hydride, polyhydride, organometallic, insertion, amide, imido, imine, phosphine", "abstract": "A series of (pentamethylcyclopentadienyl)tantalum bis(phosphine) polyhydride complexes, Cp*TaL2H4 (L = PMe3, PMe2(C6H5), P(OMe)3, and L2 dmpe; Cp* = \u03b75 - C5(CH3)5) and Cp*Ta(PMe3)2H3Cl, have been prepared by high pressure hydrogenation of Cp*TaMe4 or Cp*TaMe3Cl in the presence of L. The hydride ligands are more hydridic than protic in character. All of the compounds react with acetone and methanol to afford isopropoxide and methoxide complexes, respectively. Reactions with carbon monoxide yield carbonyl hydride and dicarbonyl compounds resulting from sequential reductive elimination of dihydrogen. Hydrogenation of ethylene is observed, as well as catalytic dimerization of ethylene to 1-butene. Most reactions of these eighteen-electron polyhydride complexes are thought to involve rate-determining loss of a phosphine ligand. Evidence is presented in support of coordination of acetone to tantalum prior to its reduction to isopropoxide. By contrast, methanol can react qirectly with the coordinatively saturatedtantalum hydride species to generate H2.
\r\n\r\nLow temperature and high field NMR spectroscopy has been used to investigate the coordination geometries of these polyhydride complexes and some niobium analogues. Using symmetry arguments, the spectra indicate a Cs structure with equivalent phosphorus atoms for complexes with monodentate phosphine ligands. This is consistent with an X-ray crystal structure of Cp*Ta(PMe3)2H4, in which the hydride ligands were not located. A different Cs structure, with inequivalent phosphorus atoms, is indicated for compounds with the bidentate dmpe ligand.
\r\n\r\nThe reactions of Cp*TaMe3Cl (1) with a variety of alkali metal alkoxide, alkylamide, and alkyl reagents have been examined. Reaction with LiNMe2 produces Cp*Ta(NMe2)Me3, but this decomposes at 25\u00b0C to an imine (or metallaazirane) complex, Cp*Ta(CH2NMe)Me2. The decomposition is a first-order, unimolecular process with a large kinetic isotope effect kH/kD = 9.7). Monoalkylamides (LiNHR) react with 1 to form imido complexes Cp*Ta(NR)Me2. Reaction of 1 with lithium diisopropylamide forms a bridging methylene complex, Cp*Me2Ta(\u00b5CH2)(\u00b5H)2TaMe2Cp*. The alkoxide compounds Cp*Ta(OR)Me3 (R = Me, CHMe2, CMe3) are very stable and decompose only over 100\u00b0C. Alkyl complexes are stable only if the alkyl group does not have \u03b2-hydrogens. The rates of hydrogen abstraction or elimination processes in this system correlate with the nature of the atom bound to tantalum: for reactions involving a \u03b2-hydrogen the order is C > N > O while \u03b1-hydrogen abstraction reactions appear to vary in the reverse order, N > C. These rates seem to reflect the thermodynamic preferences in these compounds.
\r\n\r\nHydrogenation of the imido compounds (Cp*Ta(NR)Me2) in the presence of phosphine ligands yield the first examples of imido-hydride complexes, Cp*Ta(NR)H2(L) (L = PMe3, PMe2(C6H5), R = CMe3, CH2CM3). An alkyl-hydride complex, Cp*Ta(CH2NMe)Me(PMe3)H, has also been prepared. The reaction of Cp*TaMe3(OCMe3) with hydrogen forms an unusual asymmetric dimer, Cp*(Me3CO)2HTa(\u00b5H)2 TaH3Cp*, which has been characterized by NMR and IR spectroscopies.
\r\n\r\nThe tantalum hetero-olefin complexes Cp*Ta(CH2NMe)Me2 and Cp*Ta(OCMe2)Me2 react readily with olefins, aldehydes, and nitriles. A number of five- and seven-atom metallacycles have been prepared.
", "date": "1983", "date_type": "degree", "id_number": "CaltechTHESIS:03212012-094858041", "refereed": "FALSE", "official_url": "https://resolver.caltech.edu/CaltechTHESIS:03212012-094858041", "rights": "No commercial reproduction, distribution, display or performance rights in this work are provided.", "funders": { "items": [ { "agency": "NSF" } ] }, "collection": "CaltechTHESIS", "reviewer": "Tony Diaz", "deposited_on": "2012-03-21 22:08:12", "doi": "10.7907/DR9V-G528", "divisions": { "items": [ "div_chem" ] }, "institution": "California Institute of Technology", "thesis_type": "phd", "thesis_advisor": { "items": [ { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "advisor" } ] }, "thesis_committee": { "items": [ { "email": "hbgray@caltech.edu", "id": "Gray-H-B", "name": { "family": "Gray", "given": "Harry B." }, "orcid": "0000-0002-7937-7876", "role": "chair" }, { "email": "bercaw@caltech.edu", "id": "Bercaw-J-E", "name": { "family": "Bercaw", "given": "John E." }, "role": "member" }, { "id": "Janda-K-C", "name": { "family": "Janda", "given": "Kenneth C." }, "role": "member" }, { "email": "rhg@caltech.edu", "id": "Grubbs-R-H", "name": { "family": "Grubbs", "given": "Robert H." }, "role": "member" } ] }, "thesis_degree": "PHD", "thesis_degree_grantor": "California Institute of Technology", "thesis_defense_date": "1982-07-06", "review_status": "approved", "option_major": { "items": [ "chemistry" ] }, "copyright_statement": "Author's Rights Authorization: I hereby certify that, if appropriate, I have obtained a written permission statement from the owner(s) of each third party copyrighted matter to be included in my thesis, dissertation, or project report, allowing distribution as specified below. I certify that the version I submitted here is the same as that approved by my advisory committee.\n\nI hereby grant to California Institute of Technology or its agents the non-exclusive license to archive and make accessible, under the conditions specified under \"Thesis Availability\" in this submission, my thesis, dissertation, or project report in whole or in part in all forms of media, now or hereafter known. I retain all other ownership rights to the copyright of the thesis, dissertation, or project report. I also retain the right to use in future works (such as articles or books) all or part of this thesis, dissertation, or project report.", "resource_type": "thesis", "pub_year": "1983", "author_list": "Mayer, James Moers", "advisor_list": "Janda, Kenneth C.", "comittee_list": "Gray, Harry B.; Bercaw, John E.; et el." } ]