Nuclear quantum effects in electronically adiabatic quantum time correlation functions

Application to the absorption spectrum of a hydrated electron

L. Túri, György Hantal, Peter J. Rossky, Daniel Borgis

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

A general formalism for introducing nuclear quantum effects in the expression of the quantum time correlation function of an operator in a multilevel electronic system is presented in the adiabatic limit. The final formula includes the nuclear quantum time correlation functions of the operator matrix elements, of the energy gap, and their cross terms. These quantities can be inferred and evaluated from their classical analogs obtained by mixed quantum-classical molecular dynamics simulations. The formalism is applied to the absorption spectrum of a hydrated electron, expressed in terms of the time correlation function of the dipole operator in the ground electronic state. We find that both static and dynamic nuclear quantum effects distinctly influence the shape of the absorption spectrum, especially its high energy tail related to transitions to delocalized electron states. Their inclusion does improve significantly the agreement between theory and experiment for both the low and high frequency edges of the spectrum. It does not appear sufficient, however, to resolve persistent deviations in the slow Lorentzian-like decay part of the spectrum in the intermediate 2-3 eV region.

Original languageEnglish
Article number024119
JournalThe Journal of Chemical Physics
Volume131
Issue number2
DOIs
Publication statusPublished - 2009

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Mathematical operators
Absorption spectra
absorption spectra
operators
Electrons
formalism
electrons
Electronic states
Electron transitions
electron states
electronics
Electron energy levels
Molecular dynamics
Energy gap
inclusions
analogs
dipoles
molecular dynamics
low frequencies
deviation

ASJC Scopus subject areas

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

Cite this

Nuclear quantum effects in electronically adiabatic quantum time correlation functions : Application to the absorption spectrum of a hydrated electron. / Túri, L.; Hantal, György; Rossky, Peter J.; Borgis, Daniel.

In: The Journal of Chemical Physics, Vol. 131, No. 2, 024119, 2009.

Research output: Contribution to journalArticle

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