Dynamics of molecules using semigroup techniques: Vibrational line shapes in exciton models of mixed valency

Ronnie Kosloff*, Mark A. Ratner

*Corresponding author for this work

Research output: Contribution to journalArticle

14 Citations (Scopus)

Abstract

The vibrational line shapes expected for a case of "excitation mixed valency" (defined, in analogy, to ordinary electronic mixed valency, as one exciton moving between two equivalent electronic sites) is studied using a semigroup formalism to include relaxation effects. We include the quadratic electron-vibration coupling, corresponding to frequency changes. The results demonstrate the line narrowing expected in the rapid exchange limit, but also show that similar behavior may be caused by rapid electronic excitation. The simple model is readily extended to include transfer rates and ordinary (electronic) mixed valency. The relaxation process introduced a new time scale into the problem; when this becomes of the order of other relevant time scales (transfer, vibration, barrier residence) interesting line shape phenomena may be observed.

Original languageEnglish (US)
Pages (from-to)2841-2846
Number of pages6
JournalThe Journal of Chemical Physics
Volume77
Issue number6
DOIs
StatePublished - Jan 1 1982

Fingerprint

Relaxation processes
line shape
excitons
Molecules
Electrons
electronics
molecules
vibration
excitation
formalism
LDS 751
electrons

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

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abstract = "The vibrational line shapes expected for a case of {"}excitation mixed valency{"} (defined, in analogy, to ordinary electronic mixed valency, as one exciton moving between two equivalent electronic sites) is studied using a semigroup formalism to include relaxation effects. We include the quadratic electron-vibration coupling, corresponding to frequency changes. The results demonstrate the line narrowing expected in the rapid exchange limit, but also show that similar behavior may be caused by rapid electronic excitation. The simple model is readily extended to include transfer rates and ordinary (electronic) mixed valency. The relaxation process introduced a new time scale into the problem; when this becomes of the order of other relevant time scales (transfer, vibration, barrier residence) interesting line shape phenomena may be observed.",
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Dynamics of molecules using semigroup techniques : Vibrational line shapes in exciton models of mixed valency. / Kosloff, Ronnie; Ratner, Mark A.

In: The Journal of Chemical Physics, Vol. 77, No. 6, 01.01.1982, p. 2841-2846.

Research output: Contribution to journalArticle

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