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

Borgis, Daniel; Rossky, Peter J.; Turi, László

doi:doi:10.1063/1.2780868

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Do supercooled liquids freeze by spinodal decomposition?

Two questions are addressed in this paper: Is it likely that spinodals occur in the freezing of one-component liquids at degrees of supercooling as moderate as T/Tmelt = 0.6, and are the ramified solidlike structural fluctuations seen in simulations of supercooled liquids the tell-tale harbingers of spinodal decomposition? It has been suggested in several papers that in the freezing of argonlike systems, a spinodal can be expected to be encountered at T/Tmelt of ∼ 0.6 or even at a shallower de...

Solvation shell dynamics studied by molecular dynamics simulation in relation to the translational and rotational dynamics of supercritical water and benzene

The solvation shell dynamics of supercritical water is analyzed by molecular dynamics simulation with emphasis on its relationship to the translational and rotational dynamics. The relaxation times of the solvation number (τS), the velocity autocorrelation function (τD), the angular momentum correlation function (τJ), and the second-order reorientational correlation function (τ2R) are studied at a supercritical temperature of 400 °C over a wide density region of 0.01–1.5 g cm−3. The relaxation ...

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.

Article Outline

INTRODUCTION
BACKGROUND
GAP DEPENDENT DECAY RATE
DISCUSSION AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

excited states, ground states, molecular dynamics method, potential energy surfaces, quantum chemistry, solvated electrons, solvent effects

PACS

31.50.-x

Potential energy surfaces
31.50.Df

Potential energy surfaces for excited electronic states
31.50.Bc

Potential energy surfaces for ground electronic states
31.70.Dk

Environmental and solvent effects

ARTICLE DATA

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http://dx.doi.org/10.1063/1.2780868

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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