Fast and accurate nonadiabatic molecular dynamics enabled through variational interpolation of correlated electron wavefunctions

• URL: http://arxiv.org/abs/2403.12275v2
• Date: Tue, 30 Apr 2024 21:37:03 GMT
• Title: Fast and accurate nonadiabatic molecular dynamics enabled through variational interpolation of correlated electron wavefunctions
• Authors: Kemal Atalar, Yannic Rath, Rachel Crespo-Otero, George H. Booth,
• Abstract summary: We develop a small training set of many-body wavefunctions through chemical space at mean-field cost. We show that analytic multi-state forces and nonadiabatic couplings from the model enable application to nonadiabatic molecular dynamics. This culminates in application to the nonadiabatic molecular dynamics of a photoexcited 28-atom hydrogen chain.
• Score: 0.0
• License: http://creativecommons.org/licenses/by/4.0/
• Abstract: We build on the concept of eigenvector continuation to develop an efficient multi-state method for the rigorous and smooth interpolation of a small training set of many-body wavefunctions through chemical space at mean-field cost. The inferred states are represented as variationally optimal linear combinations of the training states transferred between the many-body basis of different nuclear geometries. We show that analytic multi-state forces and nonadiabatic couplings from the model enable application to nonadiabatic molecular dynamics, developing an active learning scheme to ensure a compact and systematically improvable training set. This culminates in application to the nonadiabatic molecular dynamics of a photoexcited 28-atom hydrogen chain, with surprising complexity in the resulting nuclear motion. With just 22 DMRG calculations of training states from the low-energy correlated electronic structure at different geometries, we infer the multi-state energies, forces and nonadiabatic coupling vectors at 12,000 geometries with provable convergence to high accuracy along an ensemble of molecular trajectories, which would not be feasible with a brute force approach. This opens up a route to bridge the timescales between accurate single-point correlated electronic structure methods and timescales of relevance for photo-induced molecular dynamics.

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