TDDFT Gradients and Nonadiabatic Couplings with Minimal Auxiliary Basis Set Approximation for Fewest-Switches Surface Hopping Dynamics

TL;DR

This paper introduces an efficient GPU-accelerated TDDFT-based FSSH implementation with minimal auxiliary basis sets, significantly reducing computational costs for nonadiabatic molecular dynamics in medium-sized molecules.

Contribution

It develops a novel approach combining density fitting, minimal auxiliary basis sets, and an approximate Z-vector solver to enhance efficiency while maintaining accuracy.

Findings

Electronic structure calculations for 73-atom systems complete within one minute on a single GPU.

The approximations cause negligible errors in realistic FSSH workloads.

The method significantly accelerates nonadiabatic dynamics simulations for medium-sized molecules.

Abstract

The electronic structure calculations remain a major bottleneck in ab initio nonadiabatic molecular dynamics. We develop an efficient TDDFT-based FSSH implementation in the GPU4PySCF package for medium-sized molecular systems. Our approach combines density fitting, TDDFT with minimal auxiliary basis sets (TDDFT-ris), and an approximate Z-vector solver to reduce the computational cost of TDDFT excited states and derivative coupling calculations. These approximations introduce negligible errors in realistic FSSH workloads while maintaining high computational efficiency. Benchmark results show that, for 73-atom systems with a triple-$\zeta$ basis set, individual electronic structure calculations are completed within one minute on a single NVIDIA A100 GPU.