Fourier analysis, correlation functions and nonadiabatic electron transfer

Wavepackets and exact representations

Audrey Dell Hammerich, Abraham Nitzan, Mark A Ratner

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

We investigate the validity of several common approximations in the analysis of nonadiabatic intramolecular electron transfer rate constants. Utilizing the Fourier representation of the golden rule form, we study the evolution of the vibrational correlation function that represents the density-of-states-weighted Franck-Condon factor. In particular, we test the validity of the perturbation theoretic golden rule form and of the Gaussian wavepacket representation for the vibrational wavefunctions against numerically exact quantum mechanical propagations. Although specific cases are found in which both of these break down, for a wide range of conditions (including anharmonic behavior and frequency changes), both the Gaussian wavepacket representation and the golden rule are excellent approximations.

Original languageEnglish
Pages (from-to)383-399
Number of pages17
JournalTheoretica Chimica Acta
Volume89
Issue number5-6
DOIs
Publication statusPublished - Dec 1994

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Fourier analysis
Fourier Analysis
Wave functions
Rate constants
electron transfer
Electrons
approximation
breakdown
perturbation
propagation

Keywords

  • Correlation functions
  • Electron transfer
  • Nonadiabatic
  • Propagation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Fourier analysis, correlation functions and nonadiabatic electron transfer : Wavepackets and exact representations. / Hammerich, Audrey Dell; Nitzan, Abraham; Ratner, Mark A.

In: Theoretica Chimica Acta, Vol. 89, No. 5-6, 12.1994, p. 383-399.

Research output: Contribution to journalArticle

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