The symmetric quasi-classical model using on-the-fly time-dependent density functional theory within the Tamm-Dancoff approximation (2209.11831v1)

Abstract: The primary computational challenge when simulating nonadiabatic ab initio molecular dynamics is the unfavorable compute costs of electronic structure calculations with molecular size. Simple electronic structure theories, like time-dependent density functional theory within the Tamm-Dancoff approximation (TDDFT/TDA), alleviate this cost for moderately sized molecular systems simulated on realistic time scales. Although TDDFT/TDA does have some limitations in accuracy, an appealing feature is that, in addition to including electron correlation through the use of a density functional, the cost of calculating analytic nuclear gradients and nonadiabatic coupling vectors is often computationally feasible even for moderately-sized basis sets. In this work, some of the benefits and limitations of TDDFT/TDA are discussed and analyzed with regard to its applicability as a "back-end" electronic structure method for the symmetric quasi-classical Meyer-Miller model (SQC/MM). In order to investigate the benefits and limitations of TDDFT/TDA, SQC/MM is employed to predict and analyze a prototypical example of excited-state hydrogen transfer in gas-phase malonaldehyde. Then, the ring-opening dynamics of selenophene are simulated which highlight some of the deficiencies of TDDFT/TDA. Additionally, some new algorithms are proposed that speed up the calculation of analytic nuclear gradients and nonadiabatic coupling vectors for a set of excited electronic states.