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Dissertation Information for Amy L. Burroughs

NAME:
- Amy L. Burroughs

DEGREE:
- Ph.D.

DISCIPLINE:
- Chemistry

SCHOOL:
- Emory University (USA) (2004)

ADVISORS:
- Michael C. Heaven

COMMITTEE MEMBERS:
- Myron J. Kaufman
- Keiji Morokuma

MPACT Status: Fully Complete

Title: Caging in clusters and matrices

Abstract: The experiments presented in this dissertation were set up either to probe the cage dynamics of a particular system or to create caged environments in order to study molecules under relatively controlled conditions. An attempt was made to experimentally observe the trichlorine radical using the unique properties of a rare gas matrix. HCl-Cl 2 complexes were photolyzed in Ar and Kr matrices. Following 193 run photolysis, a rather long-lived (tens of microseconds) emission is observed at 470 nm in Ar matrices (475 nm in Kr) with laser excitation at 308 nm. The lifetime of the emission exhibits both temperature and concentration dependence and arguments are made for assigning the emission to the trichlorine anion, Cl 3 - . The A 2 Ä- X 2 Ð and B 2 Ó - - X 2 Ð transitions of CH/D were examined for radicais trapped in Ar and Kr matrices. Excitation spectra yield evidence that CH/D( B ) rotates in solid Ar and Kr. Vibrational relaxation of CH/D( B ) is faster for the heavier isotope, indicating that vibration to rotation energy transfer is the dominant mechanism. The decay of CH( B ) v = 0 is primarily radiative in both Ar and Kr, with small contributions from B [arrow right] A non-radiative transfer. Spectra for the A-X transition of CH-Ar n clusters were recorded. Comparison with the matrix data suggests that the clusters consist of CH bound to the surface of Ar n . Fluorescence depletion measurements were used to examine the one-atom cage effect in I 2 -Ar. It was concluded that the T-shaped isomer contributes less than 5% of the cage effect fluorescence. Instead, depletion via a diffuse band system previously assigned to the linear I 2 -Ar was observed. Optical-optical double resonance techniques were used to examine the dissociation dynamics of I 2 ( B )-Ar. Using rotational population distributions, the dissociation energy for the T-shaped complex was determined to be D 0 (C 2v ) = 220 cm -1 . Dissociation of linear I 2 ( B, v )-Ar was examined and observed to have a rotationally cold product distribution. The I 2 -Ne complex was examined using double resonance and fluorescence depletion techniques. Action spectra for I 2 ( B, v )-Ne revealed several previously unobserved intermolecular vibrational levels that were assigned to T-shaped, linear, or delocalized states of I 2 ( B, v )-Ne. An estimate for the dissociation energy for I 2 ( B )-Ne of D 0 = 57.6 ± 1.0 cm -1 was determined by monitoring the predissociation fragments.

MPACT Scores for Amy L. Burroughs

A = 0
C = 0
A+C = 0
T = 0
G = 0
W = 0
TD = 0
TA = 0
calculated 2008-03-22 16:09:27

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