### 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 language | English |
---|---|

Article number | 174508 |

Journal | The Journal of Chemical Physics |

Volume | 127 |

Issue number | 17 |

DOIs | |

Publication status | Published - 2007 |

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### ASJC Scopus subject areas

- Atomic and Molecular Physics, and Optics

### Cite this

*The Journal of Chemical Physics*,

*127*(17), [174508]. https://doi.org/10.1063/1.2780868

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

Research output: Contribution to journal › Article

*The Journal of Chemical Physics*, vol. 127, no. 17, 174508. https://doi.org/10.1063/1.2780868

}

TY - JOUR

T1 - Nuclear quantum effects on the nonadiabatic decay mechanism of an excited hydrated electron

AU - Borgis, Daniel

AU - Rossky, Peter J.

AU - Túri, L.

PY - 2007

Y1 - 2007

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=35948994511&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=35948994511&partnerID=8YFLogxK

U2 - 10.1063/1.2780868

DO - 10.1063/1.2780868

M3 - Article

AN - SCOPUS:35948994511

VL - 127

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 17

M1 - 174508

ER -