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Quantum mechanics of chemical reactions: Recent developments in reactive scattering and in reaction path Hamiltonians

Conference ·
OSTI ID:6047306

Two recent developments in the theory of chemical reaction dynamics are reviewed. First, it has recently been discovered that the S- matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has considerably simplified quantum mechanical reactive scattering calculations, which provide the rigorous characterizations of bimolecular reactions. Second, a new kind of reaction path Hamiltonian has been developed, one based on the ''least motion'' path that interpolates linearly between the reactant and product geometry of the molecule (rather than the previously used minimum energy, or ''intrinsic'' reaction path). The form of Hamiltonian which results is much simpler than the original reaction path Hamiltonian, but more important is the fact that it provides a more physically correct description of hydrogen atom transfer reactions. 44 refs., 4 figs.

Research Organization:
Lawrence Berkeley Lab., CA (USA)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
6047306
Report Number(s):
LBL-26377; CONF-8808219-2; ON: DE89010438
Country of Publication:
United States
Language:
English