Spectroscopic Studies of Azide compounds: Thermochemistry, Chemical Kinetics and Photodissociation Dynamics
- Degree Grantor:
- University of California, Santa Barbara. Chemistry
- Degree Supervisor:
- Alec M. Wodtke
- Place of Publication:
- [Santa Barbara, Calif.]
- Publisher:
- University of California, Santa Barbara
- Creation Date:
- 2012
- Issued Date:
- 2012
- Topics:
- Chemistry, General, Chemistry, Physical, and Physics, General
- Keywords:
- Azide,
Photodissociation,
Cyclic N3.,
Photolysis,
Photoionization, and
Matrix-isolation - Genres:
- Online resources and Dissertations, Academic
- Dissertation:
- Ph.D.--University of California, Santa Barbara, 2012
- Description:
Some of the most difficult chemical systems, either to observe or produce in significant quantities, are polynitrogen molecules. One example of this type of molecules in the early stages of investigation is cyclic-N3, whose molecular geometry and promising technological applications have attracted our attention to define optimal experimental conditions for being photoproduced. High-resolution synchrotron-radiation-based Photoionization Mass Spectrometry (PIMS) was applied to study the dissociative photoionization of three azide precursors for cyclic-N3; chlorine azide (ClN3), hydrogen azide (HN3), and methyl azide (CH3N3). In our attempts to detect cyclic-N3, the thermochemistry derived in the PIMS studies stimulated our work to perform photodissociation dynamics experiments of CH3N3 at 193 nm using Photofragment Translational Spectroscopy (PTS) with electron impact (EI) detection under collision-free conditions, and chemical kinetic studies based on Infrared Spectroscopy (IR) in matrix-isolated ices formed from rare gases (Argon, Nitrogen and Xenon). PTS experiments lead us to derive the branching ratio between reactions CH 3+N3 (radical channel) vs CH3N+N2 (molecular channel), and to conclude that cyclic-N3 is the dominant product in the radical channel. In contrast, in the matrix isolation experiments we found no evidence of the radical channel, possibly due to barrier-less recombination. However, since no mechanistic reports of methyl azide dissociation exist at these conditions, these studies could have significant implications for future experiments addressed to detect cylic-N3 under matrix environments.
- Physical Description:
- 1 online resource (222 pages)
- Format:
- Text
- Collection(s):
- UCSB electronic theses and dissertations
- Other Versions:
- http://gateway.proquest.com/openurl?url_ver=Z39.88-2004&rft_val_fmt=info:ofi/fmt:kev:mtx:dissertation&res_dat=xri:pqm&rft_dat=xri:pqdiss:3505469
- ARK:
- ark:/48907/f36t0jrd
- ISBN:
- 9781267298034
- Catalog System Number:
- 990037519110203776
- Copyright:
- Alfredo Quinto-Hernandez, 2012
- Rights:
- In Copyright
- Copyright Holder:
- Alfredo Quinto-Hernandez
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