Theoretical and Computational Chemistry

Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory

Authors

Abstract

We present the first implementation of multiconfiguration pair-density functional theory (MC-PDFT) ab initio molecular dynamics. MC-PDFT is a multireference electronic structure method that in many cases has a similar accuracy (or even better accuracy) than complete active space second order perturbation theory (CASPT2) at a significantly lower computational cost. In this work we introduced MC-PDFT analytical gradients into the SHARC molecular dynamics program for ab initio, nonadiabatic molecular dynamics simulations. We verify our implementation by examining the intersystem crossing dynamics of thioformaldehyde, and we observe excellent agreement with recent CASPT2 and experimental findings. Moreover, with MC-PDFT we could perform dynamics with an active space that was computationally too expensive for CASPT2.

Content

Thumbnail image of 10_18_21_Thioformaldehyde_V12.pdf

Supplementary material

Thumbnail image of 10_18_21_Thioformaldehyde_SI_v12.pdf
Supporting Information For: Nonadiabatic Molecular Dynamics by Multiconfiguration Pair-Density Functional Theory
Supporting Information
Thumbnail image of SI-INPUTS_AND_OUTPUTS.zip
Supporting Information for Input and Output Files
This is a tar file containing example input and output files for the calculations performed in this study.