Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol

Daniel Borgis, Peter J. Rossky, L. Túri

Research output: Contribution to journalArticle

37 Citations (Scopus)

Abstract

A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p → 5 relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.

Original languageEnglish
Article number064501
JournalThe Journal of Chemical Physics
Volume125
Issue number6
DOIs
Publication statusPublished - 2006

Fingerprint

Quantum electronics
Excited states
decay rates
Methanol
Molecular dynamics
Energy gap
methyl alcohol
Electrons
Water
Computer simulation
water
quantum electronics
life (durability)
electrons
vibration mode
molecular dynamics
formalism
predictions
excitation
simulation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

@article{757e6d038b1b4d57b3d4af281caba81f,
title = "Quantized time correlation function approach to nonadiabatic decay rates in condensed phase: Application to solvated electrons in water and methanol",
abstract = "A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p → 5 relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.",
author = "Daniel Borgis and Rossky, {Peter J.} and L. T{\'u}ri",
year = "2006",
doi = "10.1063/1.2221685",
language = "English",
volume = "125",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "6",

}

TY - JOUR

T1 - Quantized time correlation function approach to nonadiabatic decay rates in condensed phase

T2 - Application to solvated electrons in water and methanol

AU - Borgis, Daniel

AU - Rossky, Peter J.

AU - Túri, L.

PY - 2006

Y1 - 2006

N2 - A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p → 5 relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.

AB - A new, alternative form of the golden rule formula defining the nonadiabatic transition rate between two quantum states in condensed phase is presented. The formula involves the quantum time correlation function of the energy gap, of the nonadiabatic coupling, and their cross terms. Those quantities can be inferred from their classical counterparts, determined via molecular dynamics simulations. The formalism is applied to the problem of the nonadiabatic p → 5 relaxation of an equilibrated p-electron in water and methanol. We find that, in both solvents, the relaxation is induced by the coupling to the vibrational modes and the quantum effects modify the rate by a factor of 2-10 depending on the quantization procedure applied. The resulting p-state lifetime for a hypothetical equilibrium excited state appears extremely short, in the sub-100 fs regime. Although this result is in contrast with all previous theoretical predictions, we also illustrate that the lifetimes computed here are very sensitive to the simulated electronic quantum gap and to the strongly correlated nonadiabatic coupling.

UR - http://www.scopus.com/inward/record.url?scp=33747235364&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=33747235364&partnerID=8YFLogxK

U2 - 10.1063/1.2221685

DO - 10.1063/1.2221685

M3 - Article

AN - SCOPUS:33747235364

VL - 125

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 6

M1 - 064501

ER -