On application of deep learning to simplified quantum-classical dynamics in electronically excited states

Abstract

Abstract Deep learning (DL) is applied to simulate non-adiabatic molecular dynamics of phenanthrene, using the time-dependent density functional based tight binding (TD-DFTB) approach for excited states combined with mixed quantum–classical propagation. Reference calculations rely on Tully’s fewest-switches surface hopping (FSSH) algorithm coupled to TD-DFTB, which provides electronic relaxation dynamics in fair agreement with various available experimental results. Aiming at describing the coupled electron-nuclei dynamics in large molecular systems, we then examine the combination of DL for excited-state potential energy surfaces (PESs) with a simplified trajectory surface hopping propagation based on the Belyaev–Lebedev (BL) scheme. We start to assess the accuracy of the TD-DFTB approach upon comparison of the optical spectrum with experimental and higher-level theoretical results. Using the recently developed SchNetPack (Schütt et al 2019 J. Chem. Theory Comput. 15 448–55) for DL applications, we train several models and evaluate their performance in predicting excited-state energies and forces. Then, the main focus is given to the analysis of the electronic population of low-lying excited states computed with the aforementioned methods. We determine the relaxation timescales and compare them with experimental data. Our results show that DL demonstrates its ability to describe the excited-state PESs. When coupled to the simplified BL scheme considered in this study, it provides reliable description of the electronic relaxation in phenanthrene as compared with either the experimental data or the higher-level FSSH/TD-DFTB theoretical results. Furthermore, the DL performance allows high-throughput analysis at a negligible cost.