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Title: Velocity map imaging study of BrCl photodissociation at 467 nm: Determination of all odd-rank (K=1 and 3) anisotropy parameters for the Cl({sup 2}P{sub 3/2}{sup 0}) photofragments

Abstract

Resonance-enhanced multiphoton ionization and velocity map imaging of the Cl({sup 2}P{sub 3/2}{sup 0}) fragments of BrCl photolysis at 467.16 nm have been used to obtain a complete set of orientation parameters (with ranks K=1 and 3) describing the polarization of the electronic angular momentum. The experiments employ two geometries distinguished only by the circular or linear polarization of the photolysis laser beam. Normalized difference images constructed from the data accumulated using a right or left circularly polarized probe-laser beam, counterpropagating with the photolysis laser, were fitted to basis images corresponding to contributions from various odd-rank anisotropy parameters. Expressions are given for the difference images in terms of the K=1 and 3 anisotropy parameters, which describe coherent and incoherent parallel and perpendicular excitation and dissociation mechanisms. The nonzero values of the anisotropy parameters are indicative of nonadiabatic dissociation dynamics, with likely contributions from flux on the A {sup 3}{pi}(1),B {sup 3}{pi}(0{sup +}),C {sup 1}{pi}(1), and X {sup 1}{sigma}{sup +}(0{sup +}) states as well as one further {omega}=1 state, all of which correlate adiabatically to Cl({sup 2}P{sub 3/}0)+Br({sup 2}P{sub 3/2}{sup 0}) photofragments. The magnitudes of the parameters depend both on the amplitudes of dissociative flux in these states, and also on themore » phases accumulated by the nuclear wave functions for different dissociation pathways.« less

Authors:
; ; ; ; ;  [1];  [2]
  1. Ioffe Physico-Technical Institute, Russian Academy of Sciences, 194021 Saint Petersburg (Russian Federation)
  2. (United Kingdom)
Publication Date:
OSTI Identifier:
20783240
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 124; Journal Issue: 9; Other Information: DOI: 10.1063/1.2168149; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ANGULAR MOMENTUM; ANISOTROPY; BROMINE CHLORIDES; DISSOCIATION; LASERS; MULTI-PHOTON PROCESSES; PHOTOIONIZATION; PHOTOLYSIS; PHOTON-MOLECULE COLLISIONS; POLARIZATION; REACTION KINETICS; WAVE FUNCTIONS

Citation Formats

Smolin, Andrey G., Vasyutinskii, Oleg S., Vieuxmaire, Olivier P. J., Ashfold, Michael N.R., Balint-Kurti, Gabriel G., Orr-Ewing, Andrew J., and School of Chemistry, University of Bristol, Bristol BS8 1TS. Velocity map imaging study of BrCl photodissociation at 467 nm: Determination of all odd-rank (K=1 and 3) anisotropy parameters for the Cl({sup 2}P{sub 3/2}{sup 0}) photofragments. United States: N. p., 2006. Web. doi:10.1063/1.2168149.
Smolin, Andrey G., Vasyutinskii, Oleg S., Vieuxmaire, Olivier P. J., Ashfold, Michael N.R., Balint-Kurti, Gabriel G., Orr-Ewing, Andrew J., & School of Chemistry, University of Bristol, Bristol BS8 1TS. Velocity map imaging study of BrCl photodissociation at 467 nm: Determination of all odd-rank (K=1 and 3) anisotropy parameters for the Cl({sup 2}P{sub 3/2}{sup 0}) photofragments. United States. doi:10.1063/1.2168149.
Smolin, Andrey G., Vasyutinskii, Oleg S., Vieuxmaire, Olivier P. J., Ashfold, Michael N.R., Balint-Kurti, Gabriel G., Orr-Ewing, Andrew J., and School of Chemistry, University of Bristol, Bristol BS8 1TS. Tue . "Velocity map imaging study of BrCl photodissociation at 467 nm: Determination of all odd-rank (K=1 and 3) anisotropy parameters for the Cl({sup 2}P{sub 3/2}{sup 0}) photofragments". United States. doi:10.1063/1.2168149.
@article{osti_20783240,
title = {Velocity map imaging study of BrCl photodissociation at 467 nm: Determination of all odd-rank (K=1 and 3) anisotropy parameters for the Cl({sup 2}P{sub 3/2}{sup 0}) photofragments},
author = {Smolin, Andrey G. and Vasyutinskii, Oleg S. and Vieuxmaire, Olivier P. J. and Ashfold, Michael N.R. and Balint-Kurti, Gabriel G. and Orr-Ewing, Andrew J. and School of Chemistry, University of Bristol, Bristol BS8 1TS},
abstractNote = {Resonance-enhanced multiphoton ionization and velocity map imaging of the Cl({sup 2}P{sub 3/2}{sup 0}) fragments of BrCl photolysis at 467.16 nm have been used to obtain a complete set of orientation parameters (with ranks K=1 and 3) describing the polarization of the electronic angular momentum. The experiments employ two geometries distinguished only by the circular or linear polarization of the photolysis laser beam. Normalized difference images constructed from the data accumulated using a right or left circularly polarized probe-laser beam, counterpropagating with the photolysis laser, were fitted to basis images corresponding to contributions from various odd-rank anisotropy parameters. Expressions are given for the difference images in terms of the K=1 and 3 anisotropy parameters, which describe coherent and incoherent parallel and perpendicular excitation and dissociation mechanisms. The nonzero values of the anisotropy parameters are indicative of nonadiabatic dissociation dynamics, with likely contributions from flux on the A {sup 3}{pi}(1),B {sup 3}{pi}(0{sup +}),C {sup 1}{pi}(1), and X {sup 1}{sigma}{sup +}(0{sup +}) states as well as one further {omega}=1 state, all of which correlate adiabatically to Cl({sup 2}P{sub 3/}0)+Br({sup 2}P{sub 3/2}{sup 0}) photofragments. The magnitudes of the parameters depend both on the amplitudes of dissociative flux in these states, and also on the phases accumulated by the nuclear wave functions for different dissociation pathways.},
doi = {10.1063/1.2168149},
journal = {Journal of Chemical Physics},
number = 9,
volume = 124,
place = {United States},
year = {Tue Mar 07 00:00:00 EST 2006},
month = {Tue Mar 07 00:00:00 EST 2006}
}