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Title: An empirical valence bond model for constructing global potential energy surfaces for chemical reactions of polyatomic molecular systems

Abstract

An empirical valence bond (EVB) model is proposed for constructing reactive potential energy surfaces of polyatomic molecular systems. Specifically, it is shown how the exchange potential V{sub 12}(q) of the EVB model can be chosen so that the EVB potential V(q) {triple bond} 1/2(V{sub 11}(q) + V{sub 22}(q)) - ((1/2(V{sub 11}(q) - V{sub 22}(q))){sup 2} + V{sub 12}(q){sub 2}){sup 1/2} exactly reproduces the transition-state geometry, energy, and force constant matrix obtained by an independent ab initio calculation. (Here q denotes all the 3N-6 nuclear coordinates of the N-atom system, and V{sub 11} and V{sub 22} are empirical diabatic, i.e., nonreactive, potential functions that describe the reactant and product regions of the potential surface, respectively.) Application of the overall prescription to a variety of two-dimensional test potential surfaces shows that this version of the EVB model provides an excellent description of reactive potential surfaces for a wide variety of situations.

Authors:
;  [1]
  1. Lawrence Berkeley Lab., CA (USA)
Publication Date:
OSTI Identifier:
6381540
DOE Contract Number:  
AC03-76SF00098
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry; (USA)
Additional Journal Information:
Journal Volume: 94:15; Journal ID: ISSN 0022-3654
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; POLYATOMIC MOLECULES; CHEMICAL REACTIONS; CALCULATION METHODS; GEOMETRY; MATHEMATICAL MODELS; POTENTIAL ENERGY; TWO-DIMENSIONAL CALCULATIONS; ENERGY; MATHEMATICS; MOLECULES; 400201* - Chemical & Physicochemical Properties

Citation Formats

Chang, Yantyng, and Miller, W H. An empirical valence bond model for constructing global potential energy surfaces for chemical reactions of polyatomic molecular systems. United States: N. p., 1990. Web. doi:10.1021/j100378a052.
Chang, Yantyng, & Miller, W H. An empirical valence bond model for constructing global potential energy surfaces for chemical reactions of polyatomic molecular systems. United States. doi:10.1021/j100378a052.
Chang, Yantyng, and Miller, W H. Thu . "An empirical valence bond model for constructing global potential energy surfaces for chemical reactions of polyatomic molecular systems". United States. doi:10.1021/j100378a052.
@article{osti_6381540,
title = {An empirical valence bond model for constructing global potential energy surfaces for chemical reactions of polyatomic molecular systems},
author = {Chang, Yantyng and Miller, W H},
abstractNote = {An empirical valence bond (EVB) model is proposed for constructing reactive potential energy surfaces of polyatomic molecular systems. Specifically, it is shown how the exchange potential V{sub 12}(q) of the EVB model can be chosen so that the EVB potential V(q) {triple bond} 1/2(V{sub 11}(q) + V{sub 22}(q)) - ((1/2(V{sub 11}(q) - V{sub 22}(q))){sup 2} + V{sub 12}(q){sub 2}){sup 1/2} exactly reproduces the transition-state geometry, energy, and force constant matrix obtained by an independent ab initio calculation. (Here q denotes all the 3N-6 nuclear coordinates of the N-atom system, and V{sub 11} and V{sub 22} are empirical diabatic, i.e., nonreactive, potential functions that describe the reactant and product regions of the potential surface, respectively.) Application of the overall prescription to a variety of two-dimensional test potential surfaces shows that this version of the EVB model provides an excellent description of reactive potential surfaces for a wide variety of situations.},
doi = {10.1021/j100378a052},
journal = {Journal of Physical Chemistry; (USA)},
issn = {0022-3654},
number = ,
volume = 94:15,
place = {United States},
year = {1990},
month = {7}
}