Simulating the Ghost: Quantum Dynamics of the Solvated Electron

26 June 2020, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The nature of bulk hydrated electron has been a challenge for both experiment and theory due to its short life time and high reactivity, and the need for a high-level of electronic structure theory to achieve predictive accuracy. The lack of a classical atomistic structural formula makes it exceedingly difficult to model the solvated electron using conventional empirical force fields, which describe the system in terms of interactions between point particles associated with atomic nuclei. Here we overcome this problem using a machine-learning model, that is sufficiently flexible to describe the effect of the excess electron on the structure of the surrounding water, without including the electron in the model explicitly. The resulting potential is not only able to reproduce the stable cavity structure, but also recovers the correct localization dynamics that follows the injection of an electron in neat water. The machine learning model achieves the accuracy of the state-of-the-art correlated wave function method it is trained on. It is sufficiently inexpensive to afford a full quantum statistical and dynamical description, and allows us to achieve a highly accurate determination of the structure, diffusion mechanisms and vibrational spectroscopy of the solvated electron

Keywords

Solvated Electron Dynamics
PIMD simulations
Møller–Plesset second order (MP2) perturbation theory
machine-learning-based interatomic

Supplementary materials

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SI Quantum Dynamics of the Solvated Electron
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Movie S1 localization
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Movie S2 trans dif
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