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MO: Fachverband Molekülphysik
MO 30: Molecular Spectroscopy and Theoretical Approaches
MO 30.5: Vortrag
Freitag, 14. März 2025, 15:30–15:45, HS XVI
The connection between the Exact Factorization and the Born-Huang representation of the molecular wave function — •Peter Schürger1, Yorick Lassmann2, Federica Agostini1, and Basile Curchod2 — 1Institut de Chimie Physique, University Paris-Saclay — 2Centre for Computational Chemistry, School of Chemistry, University of Bristol
In recent years, the exact factorization (EF) formalism sparked a lot of interest in the non-adiabatic dynamics community and lead to the development of various new promising methods for non-adiabatic molecular dynamics simulations [see e.g. PCCP, 26, 26693-26718 (2024)]. In EF, the molecular wave function is written as a product of a time-dependent conditional and time-dependent marginal amplitude. The EF is usually presented as ``qualitatively'' different in its formalism, compared to the more traditional Born--Huang (BH) representation, i.e. the adiabatic representation of the molecular wave function [JPC A, 126, 1263-1282 (2022)]. Here, I will present a new perspective on the foundations of EF [ChemRxiv (2024)], that does not rely on a probabilistic interpretation and that strengthens the connection between EF and BH. Specifically, EF is a basis set that can be derived from BH and the adiabatic basis by introducing a time-dependent unitary transformation. Features of the EF, like the partial normalization condition and the gauge freedom, arise naturally in our formalism. Furthermore, equations of motion can be derived in this EF basis. I will conclude by presenting some applications of EF to simulate the ultrafast dynamics of fulvene and 4-(dimethylamino)benzonitrile (DMABN).
Keywords: Exact factorization; Born-Huang expansion; Non-adiabatic Quantum Dynamics