Nuclear quantum effects in electronically adiabatic quantum time correlation functions: Application to the absorption spectrum of a hydrated electron

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

doi:doi:10.1063/1.3173276

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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.

Article Outline

INTRODUCTION
ADIABATIC QUANTUM TIME CORRELATION FUNCTIONS
APPLICATION TO THE ABSORPTION SPECTRUM OF A SOLVATED ELECTRONIC SYSTEM
1. Theoretical expression of the absorption spectrum
2. Application to the hydrated electron: Mixed quantum-classical adiabatic molecular dynamics simulations
3. Classical spectrum
4. Quantized spectra
DISCUSSION AND CONCLUSIONS

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KEYWORDS and PACS

Keywords

energy gap, ground states, liquid theory, molecular dynamics method, solvated electrons, solvation, spectrochemical analysis

PACS

61.20.Ja

Computer simulation of liquid structure
82.80.Dx

Analytical methods involving electronic spectroscopy

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http://dx.doi.org/10.1063/1.3173276

PUBLICATION DATA

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0021-9606 (print)

1089-7690 (online)

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American Institute of Physics

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