A direct test of the vibrationally adiabatic theory of chemical reactions

J. M. Bowman, Aron Kuppermann, J. T. Adams, Donald G. Truhlar

Research output: Contribution to journalArticlepeer-review

23 Scopus citations

Abstract

The adiabaticity assumption of the vibrationally adiabatic theory of chemical reactions in the zero-curvature approximation is directly tested for the collinear H + H2 reaction against calculations using exact wavefunctions. It is found that the symmetric stretch motion of the transition state is adiabatic to within 10% for total energies E ranging from 0.51 eV to 0.72 eV. For E below the zero-point energy of this symmetric stretch motion non-adiabaticity is substantial and is probably due to tunneling. For E above the first excited vibrational state energy of this symmetric stretch motion the adiabaticity assumption breaks down completely.

Original languageEnglish (US)
Pages (from-to)229-232
Number of pages4
JournalChemical Physics Letters
Volume20
Issue number3
DOIs
StatePublished - Jun 1 1973

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