Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron

Daniel Borgis, Peter J. Rossky, L. Túri

Research output: Contribution to journalArticle

26 Citations (Scopus)

Abstract

We present a kinetic analysis of the nonadiabatic decay mechanism of an excited state hydrated electron to the ground state. The theoretical treatment is based on a quantized, gap dependent golden rule rate constant formula which describes the nonadiabatic transition rate between two quantum states. The rate formula is expressed in terms of quantum time correlation functions of the energy gap and of the nonadiabatic coupling. These gap dependent quantities are evaluated from three different sets of mixed quantum-classical molecular dynamics simulations of a hydrated electron equilibrated (a) in its ground state, (b) in its first excited state, and (c) on a hypothetical mixed potential energy surface which is the average of the ground and the first excited electronic states. The quantized, gap dependent rate results are applied in a phenomenological kinetic equation which provides the survival probability function of the excited state electron. Although the lifetime of the equilibrated excited state electron is computed to be very short (well under 100 fs), the survival probability function for the nonequilibrium process in pump-probe experiments yields an effective excited state lifetime of around 300 fs, a value that is consistent with the findings of several experimental groups and previous theoretical estimates.

Original languageEnglish
Article number174508
JournalThe Journal of Chemical Physics
Volume127
Issue number17
DOIs
Publication statusPublished - 2007

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Excited states
Electrons
decay
excitation
electrons
Ground state
life (durability)
Potential energy surfaces
Kinetics
ground state
Electronic states
kinetic equations
Molecular dynamics
Rate constants
Energy gap
potential energy
Pumps
pumps
molecular dynamics
probes

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron. / Borgis, Daniel; Rossky, Peter J.; Túri, L.

In: The Journal of Chemical Physics, Vol. 127, No. 17, 174508, 2007.

Research output: Contribution to journalArticle

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