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Dissertation Information for Anatoly V. Komissarov

NAME:
- Anatoly V. Komissarov

DEGREE:
- Ph.D.

DISCIPLINE:
- Chemistry

SCHOOL:
- Emory University (USA) (2003)

ADVISORS:
- Michael C. Heaven

COMMITTEE MEMBERS:
- Keiji Morokuma
- Ming-Chang Lin

MPACT Status: Fully Complete

Title: Kinetic and spectroscopic studies of metastable species

Abstract: Photolysis of ClN 3 and the kinetics of NCl(a) and NCl(X) were investigated. Rate constants for quenching of NCl(a) by O 2 , H 2 , Cl 2 , HCl, I 2 and ClN 3 were determined. Quenching of NCl(a) by I 2 was found to be a reactive process that liberates atomic 1. Removal of NCl(a) by self-annihilation was examined and a self-annihilation rate constant of (7.0 ± 1.5) × 10 -13 cm 3 s -1 was determined. Time-resolved NCl( X ) concentration profiles were recorded following 193 and 248 nm photolysis of ClN 3 . From the NCl(a) quenching by O 2 a lower bound of 70% for branching ratio NCIl(a)/NCl was determined. Photodissociation dynamics of ClN 3 near 203 nm was studied under collision free conditions. Two photon ionization followed by ion decomposition and one photon photolysis were investigated. Thermodynamic data derived from those measurements showed a good agreement with each other and other measurements. The NCl(a)/NCl(X) branching ratio (0.77/0.23) in the UV photolysis of ClN 3 near 203 nm was obtained. I 2 (A \' ) quenching by H 2 O and O 2 (X) was studied and a revised kinetic model for the I 2 dissociation process in the COIL laser was proposed, based on the active participation of electronically excited I 2 . I* quenching kinetics by Cl 2 and Cl atoms were characterized over the temperature range from 297-663 K. The rate constant for quenching by Cl atoms was found to be almost independent of temperature, while the Cl 2 rate constant increased by three orders of magnitude in going from 297 to 663 K. Dissociation of I 2 by atomic oxygen and I*+O quenching have also been investigated. Preliminary results put an upper bound of 5 × 10 -12 cm 3 s -1 for I* quenching by oxygen atoms. The rovibronic structure of CH/D(A)-Ar has been examined by recording rotationally resolved spectra for the A-X transition. The spectra are dominated by vibrational progressions of the intermolecular stretch in combination with two bending states. Rotational energy level patterns were consistent with a linear equilibrium geometry for CH( A )-Ar. From the range of bound levels observed for the excited state, a lower bound for the dissociation energy of D 0 \' > 70 cm -1 was determined for CH( A )-Ar.

MPACT Scores for Anatoly V. Komissarov

A = 0
C = 0
A+C = 0
T = 0
G = 0
W = 0
TD = 0
TA = 0
calculated 2008-03-23 20:37:23

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