Rate constant turnovers

Energy spacings and mixings

Ronnie Kosloff, Mark A Ratner

Research output: Contribution to journalArticle

12 Citations (Scopus)

Abstract

The golden rule predicts that rate constants are proportional to the squares of mixing matrix elements divided by squared energy differences. As physical problems scale between different coupling limits, the calculated rate constant could first increase with mixing strength, reach a maximum, and then decrease as the mixing strength becomes larger. We demonstrate this general rate behavior as a function of Hamiltonian parameters, both for simple Huckel-type models and for a two-site Hubbard system. We demonstrate that the optical susceptibility in a two-site tunneling problem also shows such behavior. Such turnover phenomena appear to be quite general, as is suggested by scaling arguments.

Original languageEnglish
Pages (from-to)8479-8483
Number of pages5
JournalJournal of Physical Chemistry B
Volume106
Issue number33
DOIs
Publication statusPublished - Aug 22 2002

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Rate constants
spacing
Hamiltonians
energy
magnetic permeability
scaling
matrices

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Rate constant turnovers : Energy spacings and mixings. / Kosloff, Ronnie; Ratner, Mark A.

In: Journal of Physical Chemistry B, Vol. 106, No. 33, 22.08.2002, p. 8479-8483.

Research output: Contribution to journalArticle

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