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Title: Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions

Abstract

The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus]], NCO[sup [minus]] and NCS[sup [minus]]. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH[sub 3]0H,F + C[sub 2]H[sub 5]OH,F + OH and F + H[sub 2]. A time dependent framework for the simulation and interpretation of the bound [yields] free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH [yields] O([sup 3]P, [sup 1]D) + HF and F + H[sub 2]. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given bymore » the time autocorrelation function. For the benchmark F + H[sub 2] system, comparisons with three-dimensional quantum calculations are made.« less

Authors:
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE; USDOD; USDOE, Washington, DC (United States); Department of Defense, Washington, DC (United States)
OSTI Identifier:
6716986
Report Number(s):
LBL-33328
ON: DE93007669; CNN: AFOSR-91-0084
DOE Contract Number:  
AC03-76SF00098
Resource Type:
Technical Report
Resource Relation:
Other Information: Thesis (Ph.D.)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 74 ATOMIC AND MOLECULAR PHYSICS; CHEMICAL REACTION KINETICS; PHOTOELECTRON SPECTROSCOPY; MOLECULES; ANGULAR DISTRIBUTION; ANIONS; BROMINE; CHEMICAL REACTIONS; CHLORINE; FLUORINE; HYDRIODIC ACID; HYDROCARBONS; HYDROGEN; QUANTUM MECHANICS; CHARGED PARTICLES; DISTRIBUTION; ELECTRON SPECTROSCOPY; ELEMENTS; HALOGEN COMPOUNDS; HALOGENS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; IODINE COMPOUNDS; IONS; KINETICS; MECHANICS; NONMETALS; ORGANIC COMPOUNDS; REACTION KINETICS; SPECTROSCOPY; 400201* - Chemical & Physicochemical Properties; 400102 - Chemical & Spectral Procedures; 664400 - Experimentally Derived Information on Atomic & Molecular Properties- (1992-)

Citation Formats

Bradforth, S E. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions. United States: N. p., 1992. Web. doi:10.2172/6716986.
Bradforth, S E. Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions. United States. https://doi.org/10.2172/6716986
Bradforth, S E. 1992. "Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions". United States. https://doi.org/10.2172/6716986. https://www.osti.gov/servlets/purl/6716986.
@article{osti_6716986,
title = {Bimolecular reaction dynamics from photoelectron spectroscopy of negative ions},
author = {Bradforth, S E},
abstractNote = {The transition state region of a neutral bimolecular reaction may be experimentally investigated by photoelectron spectroscopy of an appropriate negative ion. The photoelectron spectrum provides information on the spectroscopy and dynamics of the short lived transition state and may be used to develop model potential energy surfaces that are semi-quantitative in this important region. The principles of bound [yields] bound negative ion photoelectron spectroscopy are illustrated by way of an example: a full analysis of the photoelectron bands of CN[sup [minus]], NCO[sup [minus]] and NCS[sup [minus]]. Transition state photoelectron spectra are presented for the following systems Br + HI, Cl + HI, F + HI, F + CH[sub 3]0H,F + C[sub 2]H[sub 5]OH,F + OH and F + H[sub 2]. A time dependent framework for the simulation and interpretation of the bound [yields] free transition state photoelectron spectra is subsequently developed and applied to the hydrogen transfer reactions Br + HI, F + OH [yields] O([sup 3]P, [sup 1]D) + HF and F + H[sub 2]. The theoretical approach for the simulations is a fully quantum-mechanical wave packet propagation on a collinear model reaction potential surface. The connection between the wavepacket time evolution and the photoelectron spectrum is given by the time autocorrelation function. For the benchmark F + H[sub 2] system, comparisons with three-dimensional quantum calculations are made.},
doi = {10.2172/6716986},
url = {https://www.osti.gov/biblio/6716986}, journal = {},
number = ,
volume = ,
place = {United States},
year = {Sun Nov 01 00:00:00 EST 1992},
month = {Sun Nov 01 00:00:00 EST 1992}
}