Semiclassical Nonadiabatic Molecular Dynamics Using Linearized Pair-Density Functional Theory

Abstract

Nonadiabatic molecular dynamics is an effective method for modeling nonradiative decay in electronically excited molecules. Its accuracy depends strongly on the quality of the potential energy surfaces, and its affordability for long direct-dynamic simulations with adequate ensemble averaging depends strongly on the cost of the required electronic structure calculations. Linearized pair-density functional theory (L-PDFT) is a recently developed post-self-consistent field multireference method that can model potential energy surfaces with an accuracy similar to expensive multireference perturbation theories but at a computational cost similar to the underlying multiconfiguration self-consistent field method. Here we integrate the SHARC dynamics and PySCF electronic structure code to utilize L-PDFT for electronically nonadiabatic calculations and use the combined programs to study the photoisomerization reaction of cis-azomethane. We show that L-PDFT is able to successfully simulate the photoisomerization and yields results similar to the more expensive extended multi-state complete active space second-order perturbation theory. This shows that L-PDFT can model internal conversion, and it demonstrates its promise for broader photodynamics applications.

8 pages, 5 figures

References in corpus (3)

• Libxc: a library of exchange and correlation functionals for density functional theory
• Which Electronic Structure Method to Choose in Trajectory Surface Hopping Dynamics Simulations? Azomethane as a Case Study
• Analytic Nuclear Gradients for Complete Active Space Linearized Pair-Density Functional Theory

Cited by in corpus (3)

• Nonadiabatic Field: A Conceptually Novel Approach for Nonadiabatic Quantum Molecular Dynamics
• Weighted Active Space Protocol for Multireference Machine-Learned Potentials
• MC-PDFT Nuclear Gradients and L-PDFT Energies with Meta and Hybrid Meta On-Top Functionals for Ground- and Excited-State Geometry Optimization and Vertical Excitation Energies