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Transition structure in a diabatic surface formalism
Author(s) -
Bernardi Fernando,
McDouall Joseph J.W.,
Robb Michael A.
Publication year - 1987
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.540080405
Subject(s) - diabatic , wave function , superposition principle , valence bond theory , formalism (music) , conical intersection , atomic orbital , physics , valence (chemistry) , intersection (aeronautics) , quantum mechanics , atomic physics , chemistry , potential energy , adiabatic process , art , musical , visual arts , electron , engineering , aerospace engineering
The theory of an implementation of the diabatic surface model within the Heitler–London valence bond approach is described. It is shown that the HL – VB wave function can be obtained from a Van‐Vleck transformation of an MC – SCF wave function which has been built from atom‐localized orbitals. This wave function is built from a superposition of two diabatic components, reactantlike and productlike. The transition structure is then obtained as the minimum of the seam of intersection of the diabatic surfaces and the algorithm for performing this constrained optimization is described. Several areas of application are also discussed.