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

Journal Article · Tue Mar 07 04:00:00 EST 2006 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2168149· OSTI ID:20783240

Smolin, Andrey G; Vasyutinskii, Oleg S; Vieuxmaire, Olivier P. J.; Ashfold, Michael N.R.; Balint-Kurti, Gabriel G; Orr-Ewing, Andrew J ^[1]

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1. Ioffe Physico-Technical Institute, Russian Academy of Sciences, 194021 Saint Petersburg (Russian Federation)

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.

• OSTI ID: 20783240
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 9 Vol. 124; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

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