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Title: Adiabatic three-dimensional simulations of the IHI sup minus , BrHI sup minus , and BrHBr sup minus photoelectron spectra

Abstract

In order to better characterize the transition-state region for the I + HI, Br + HI, and Br + HBr reactions, the photoelectron spectra of IHI{sup {minus}}, IDI{sup {minus}}, BrHI{sup {minus}}, BrHBr{sup {minus}}, and BrDBr{sup {minus}} have been simulated using a three-dimensional adiabatic approach. This method of simulation uses a Born--Oppenheimer separation in time scales between the fast hydrogen-atom motion and the slow halogen-atom motion to greatly simplify the computation of the photoelectron spectrum. The resulting simulations are compared to the experimental photoelectron and threshold photodetachment spectra of these anions, and to exact'' simulations of the IHI{sup {minus}} and IDI{sup {minus}} spectra. The comparison with the exact simulations shows that the adiabatic method is reasonably accurate, and is a considerable improvement over previous approximate simulation schemes. Potential-energy surfaces for the I + HI and Br + HI reactions are evaluated based on a comparison between the simulated and experimental spectra. A three-dimensional surface for the Br + HBr reaction that reproduces the experimental photoelectron spectrum is constructed by extending a fitted collinear surface to three dimensions.

Authors:
;  [1]
  1. (Department of Chemistry, University of California, Berkeley, California 94720 (United States) Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (United States))
Publication Date:
OSTI Identifier:
7039060
DOE Contract Number:  
AC03-76SF00098
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics; (United States)
Additional Journal Information:
Journal Volume: 97:2; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BROMINE; CHEMICAL REACTIONS; BROMINE COMPLEXES; PHOTOELECTRON SPECTROSCOPY; HYDRIODIC ACID; HYDROBROMIC ACID; IODINE; IODINE COMPLEXES; MOLECULAR IONS; ADIABATIC APPROXIMATION; ANIONS; ATOM-MOLECULE COLLISIONS; SIMULATION; THREE-DIMENSIONAL CALCULATIONS; ATOM COLLISIONS; BROMINE COMPOUNDS; CHARGED PARTICLES; COLLISIONS; COMPLEXES; ELECTRON SPECTROSCOPY; ELEMENTS; HALOGEN COMPOUNDS; HALOGENS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; IODINE COMPOUNDS; IONS; MOLECULE COLLISIONS; NONMETALS; SPECTROSCOPY; 400201* - Chemical & Physicochemical Properties

Citation Formats

Metz, R.B., and Neumark, D.M. Adiabatic three-dimensional simulations of the IHI sup minus , BrHI sup minus , and BrHBr sup minus photoelectron spectra. United States: N. p., 1992. Web. doi:10.1063/1.463199.
Metz, R.B., & Neumark, D.M. Adiabatic three-dimensional simulations of the IHI sup minus , BrHI sup minus , and BrHBr sup minus photoelectron spectra. United States. doi:10.1063/1.463199.
Metz, R.B., and Neumark, D.M. Wed . "Adiabatic three-dimensional simulations of the IHI sup minus , BrHI sup minus , and BrHBr sup minus photoelectron spectra". United States. doi:10.1063/1.463199.
@article{osti_7039060,
title = {Adiabatic three-dimensional simulations of the IHI sup minus , BrHI sup minus , and BrHBr sup minus photoelectron spectra},
author = {Metz, R.B. and Neumark, D.M.},
abstractNote = {In order to better characterize the transition-state region for the I + HI, Br + HI, and Br + HBr reactions, the photoelectron spectra of IHI{sup {minus}}, IDI{sup {minus}}, BrHI{sup {minus}}, BrHBr{sup {minus}}, and BrDBr{sup {minus}} have been simulated using a three-dimensional adiabatic approach. This method of simulation uses a Born--Oppenheimer separation in time scales between the fast hydrogen-atom motion and the slow halogen-atom motion to greatly simplify the computation of the photoelectron spectrum. The resulting simulations are compared to the experimental photoelectron and threshold photodetachment spectra of these anions, and to exact'' simulations of the IHI{sup {minus}} and IDI{sup {minus}} spectra. The comparison with the exact simulations shows that the adiabatic method is reasonably accurate, and is a considerable improvement over previous approximate simulation schemes. Potential-energy surfaces for the I + HI and Br + HI reactions are evaluated based on a comparison between the simulated and experimental spectra. A three-dimensional surface for the Br + HBr reaction that reproduces the experimental photoelectron spectrum is constructed by extending a fitted collinear surface to three dimensions.},
doi = {10.1063/1.463199},
journal = {Journal of Chemical Physics; (United States)},
issn = {0021-9606},
number = ,
volume = 97:2,
place = {United States},
year = {1992},
month = {7}
}