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Title: On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. I. CH[sub 3]SH[r arrow]CH[sub 3]S+H and CH[sub 3]+SH

Abstract

Recent experimental/theoretical studies have demonstrated efficient photodissociation of CH[sub 3]SH to CH[sub 3]S+H and to CH[sub 3]+SH. Avoided crossings have been implicated in the photodissociation process. This work demonstrates the existence of a surface of conical intersections of two states of the same symmetry relevant to the photodissociation offering new insights into the mechanism of the decomposition process. Using wave functions comprised of greater than 1.3 million configuration state functions convincing evidence is provided that the surface of conical intersections is a property of the system rather the particular expansion employed in this work. The conical intersections are determined [ital directly], that is without prior determination of the potential energy surfaces in question.

Authors:
 [1]
  1. (Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218 (United States))
Publication Date:
OSTI Identifier:
5279605
DOE Contract Number:  
FG02-91ER14189
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; (United States); Journal Volume: 100:5
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ORGANIC SULFUR COMPOUNDS; PHOTOLYSIS; THIOLS; DISSOCIATION; HYDROGEN; HYDROGEN SULFIDES; CHALCOGENIDES; CHEMICAL REACTIONS; DECOMPOSITION; ELEMENTS; HYDROGEN COMPOUNDS; NONMETALS; ORGANIC COMPOUNDS; PHOTOCHEMICAL REACTIONS; SULFIDES; SULFUR COMPOUNDS; 400500* - Photochemistry

Citation Formats

Yarkony, D.R.. On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. I. CH[sub 3]SH[r arrow]CH[sub 3]S+H and CH[sub 3]+SH. United States: N. p., 1994. Web. doi:10.1063/1.466351.
Yarkony, D.R.. On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. I. CH[sub 3]SH[r arrow]CH[sub 3]S+H and CH[sub 3]+SH. United States. doi:10.1063/1.466351.
Yarkony, D.R.. Tue . "On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. I. CH[sub 3]SH[r arrow]CH[sub 3]S+H and CH[sub 3]+SH". United States. doi:10.1063/1.466351.
@article{osti_5279605,
title = {On the role of conical intersections of two potential energy surfaces of the same symmetry in photodissociation. I. CH[sub 3]SH[r arrow]CH[sub 3]S+H and CH[sub 3]+SH},
author = {Yarkony, D.R.},
abstractNote = {Recent experimental/theoretical studies have demonstrated efficient photodissociation of CH[sub 3]SH to CH[sub 3]S+H and to CH[sub 3]+SH. Avoided crossings have been implicated in the photodissociation process. This work demonstrates the existence of a surface of conical intersections of two states of the same symmetry relevant to the photodissociation offering new insights into the mechanism of the decomposition process. Using wave functions comprised of greater than 1.3 million configuration state functions convincing evidence is provided that the surface of conical intersections is a property of the system rather the particular expansion employed in this work. The conical intersections are determined [ital directly], that is without prior determination of the potential energy surfaces in question.},
doi = {10.1063/1.466351},
journal = {Journal of Chemical Physics; (United States)},
number = ,
volume = 100:5,
place = {United States},
year = {Tue Mar 01 00:00:00 EST 1994},
month = {Tue Mar 01 00:00:00 EST 1994}
}