Fast and accurate nonadiabatic molecular dynamics enabled through variational interpolation of correlated electron wavefunctions
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| Format: | Preprint |
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2024
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| _version_ | 1866929332081917952 |
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| author | Atalar, Kemal Rath, Yannic Crespo-Otero, Rachel Booth, George H. |
| author_facet | Atalar, Kemal Rath, Yannic Crespo-Otero, Rachel Booth, George H. |
| contents | 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. |
| format | Preprint |
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arxiv_https___arxiv_org_abs_2403_12275 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Fast and accurate nonadiabatic molecular dynamics enabled through variational interpolation of correlated electron wavefunctions Atalar, Kemal Rath, Yannic Crespo-Otero, Rachel Booth, George H. Chemical Physics Strongly Correlated Electrons Computational Physics Quantum Physics 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. |
| title | Fast and accurate nonadiabatic molecular dynamics enabled through variational interpolation of correlated electron wavefunctions |
| topic | Chemical Physics Strongly Correlated Electrons Computational Physics Quantum Physics |
| url | https://arxiv.org/abs/2403.12275 |