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Field theory of chemical reactions. I. Ideal space representation of A + BC → AC + B processes
Author(s) -
Varracchio E. Ficocelli
Publication year - 1985
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560270103
Subject(s) - hamiltonian (control theory) , unitary state , unitary transformation , physics , chemistry , theoretical physics , computational chemistry , statistical physics , classical mechanics , quantum mechanics , mathematics , quantum , mathematical optimization , political science , law
A new quantal approach to the problem of chemical reactions, of the type A + BC → AC + B , is proposed. The general formalism is based on a change of representation for the Hamiltonian system, such that in the new (ideal space) representation the transformed Hamiltonian may present, simultaneously, information on both the “reactants” and the “products” of the dynamical process. The change of representation is carried out by means of a unitary transformation that physically corresponds to creating bound BC and AC molecules, respectively, starting from free atoms. The transformation is explicitly realized by using models available in the literature, and the ideal space Hamiltonian is fully obtained, showing that it contains, in its structure, all the channels (inelastic, reactive, dissociative, etc.) available to the system. A discussion of the dynamics, at the light of the new Hamiltonian, seems to indicate that the theory will be particularly suited for numerical applications to the problem of chemical reactions and, more generally, that it may lead to a “unified” approach for both the subreactive and rearrangement regimes, in atom‐diatom encounters.