Machine learning the Hohenberg-Kohn map for molecular excited states

Yuanming Bai, Leslie Vogt-Maranto, Mark E. Tuckerman and William J. Glover ()
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Yuanming Bai: NYU Shanghai
Leslie Vogt-Maranto: New York University
Mark E. Tuckerman: NYU-ECNU Center for Computational Chemistry at NYU Shanghai
William J. Glover: NYU Shanghai

Nature Communications, 2022, vol. 13, issue 1, 1-10

Abstract: Abstract The Hohenberg-Kohn theorem of density-functional theory establishes the existence of a bijection between the ground-state electron density and the external potential of a many-body system. This guarantees a one-to-one map from the electron density to all observables of interest including electronic excited-state energies. Time-Dependent Density-Functional Theory (TDDFT) provides one framework to resolve this map; however, the approximations inherent in practical TDDFT calculations, together with their computational expense, motivate finding a cheaper, more direct map for electronic excitations. Here, we show that determining density and energy functionals via machine learning allows the equations of TDDFT to be bypassed. The framework we introduce is used to perform the first excited-state molecular dynamics simulations with a machine-learned functional on malonaldehyde and correctly capture the kinetics of its excited-state intramolecular proton transfer, allowing insight into how mechanical constraints can be used to control the proton transfer reaction in this molecule. This development opens the door to using machine-learned functionals for highly efficient excited-state dynamics simulations.

Date: 2022
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DOI: 10.1038/s41467-022-34436-w

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