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PHOTODISSOCIATION DYNAMICS
OF GROUP V HYDRIDES
by
William P. Schroeder
A Dissertation Presented to the
FACULTY OF THE USC GRADUATE SCHOOL
UNIVERSITY OF SOUTHERN CALIFORNIA
In Partial Fulfillment of the
Requirements for the Degree
DOCTOR OF PHILOSOPHY
(CHEMISTRY)
May 2013
Copyright 2013 William P. Schroeder
i
Object Description
| Title | Photodissociation dynamics of group V hydrides |
| Author | Schroeder, William P. |
| Author email | wschroed@usc.edu;wm.schroeder1@gmail.com |
| Degree | Doctor of Philosophy |
| Document type | Dissertation |
| Degree program | Chemistry (Chemical Physics) |
| School | College of Letters, Arts And Sciences |
| Date defended/completed | 2012-12-14 |
| Date submitted | 2013-01-30 |
| Date approved | 2013-01-30 |
| Restricted until | 2013-01-30 |
| Date published | 2013-01-30 |
| Advisor (committee chair) | Wittig, Curt F. |
| Advisor (committee member) |
Flood, Thomas Kresin, Vitaly V. |
| Abstract | This dissertation discusses the ultraviolet photodissociation dynamics and compares important molecular properties of the group-V hydrides (NH₃, PH₃, SbH₃, and BiH₃). High-n Rydberg time-of-flight (HRTOF) spectroscopy has been used to study the 193.3 nm photolysis of AsH₃. The center-of-mass (c.m.) translational energy distribution for the one-photon process, AsH₃ + hv --> AsH₂ + H, P(Ec.m.), indicates that AsH₂ internal excitation accounts for ~ 64% of the available energy [i.e., hv – D₀(H₂As-H)]. Secondary AsH₂ photodissociation also takes place. Analyses of superimposed structure atop the broad P(Ec.m.) distribution suggest that AsH₂ is formed with significant a-axis rotation as well as bending excitation. Comparison of the results obtained with AsH₃ versus those of the lighter group-V hydrides (NH₃, PH₃) lends support to the proposed mechanisms. Of the group-V hydrides, AsH₃ lies intermediate between the nonrelativistic and relativistic regimes, requiring high-level electronic structure theory. ❧ The room temperature absorption spectrum of SbH3 has been recorded. The absorption spectrum is a broad continuum with no discernible structure; however, a long- wavelength tail is evident. The HRTOF technique has also been used to investigate the photodissociation dynamics of SbH₃ following 193.3 nm photolysis. The overall shapes of the translational energy distributions were inconsistent, precluding confident analysis. In spite of this, it is apparent that SbH₂ products are formed with substantial internal excitation and secondary photodissociation occurs. These general observations are consistent with the results obtained for AsH₃. |
| Keyword | photodissociation dynamics; time of flight; arsine; arsenic trihydride; molecular dynamics |
| Language | English |
| Part of collection | University of Southern California dissertations and theses |
| Publisher (of the original version) | University of Southern California |
| Place of publication (of the original version) | Los Angeles, California |
| Publisher (of the digital version) | University of Southern California. Libraries |
| Provenance | Electronically uploaded by the author |
| Type | texts |
| Legacy record ID | usctheses-m |
| Contributing entity | University of Southern California |
| Rights | Schroeder, William P. |
| Physical access | The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the author, as the original true and official version of the work, but does not grant the reader permission to use the work if the desired use is covered by copyright. It is the author, as rights holder, who must provide use permission if such use is covered by copyright. The original signature page accompanying the original submission of the work to the USC Libraries is retained by the USC Libraries and a copy of it may be obtained by authorized requesters contacting the repository e-mail address given. |
| Repository name | University of Southern California Digital Library |
| Repository address | USC Digital Library, University of Southern California, University Park Campus MC 7002, 106 University Village, Los Angeles, California 90089-7002, USA |
| Repository email | cisadmin@dots.usc.edu |
| Archival file | uscthesesreloadpub_Volume6/etd-SchroederW-1417.pdf |
Description
| Title | Page 1 |
| Contributing entity | University of Southern California |
| Repository email | cisadmin@dots.usc.edu |
| Full text | PHOTODISSOCIATION DYNAMICS OF GROUP V HYDRIDES by William P. Schroeder A Dissertation Presented to the FACULTY OF THE USC GRADUATE SCHOOL UNIVERSITY OF SOUTHERN CALIFORNIA In Partial Fulfillment of the Requirements for the Degree DOCTOR OF PHILOSOPHY (CHEMISTRY) May 2013 Copyright 2013 William P. Schroeder i |
