Ab Initio Nonadiabatic Molecular Dynamics with Hole-Hole Tamm-Dancoff Approximated Density Functional Theory

Jimmy K Yu; Christoph Bannwarth; Edward G Hohenstein; Todd J Martínez

doi:10.1021/acs.jctc.0c00644

Ab Initio Nonadiabatic Molecular Dynamics with Hole-Hole Tamm-Dancoff Approximated Density Functional Theory

J Chem Theory Comput. 2020 Sep 8;16(9):5499-5511. doi: 10.1021/acs.jctc.0c00644. Epub 2020 Aug 20.

Authors

Jimmy K Yu^{1

2

3}, Christoph Bannwarth^{2

3}, Edward G Hohenstein^{2

3}, Todd J Martínez^{1

2

3}

Affiliations

¹ Biophysics Program, Stanford University, Stanford, California 94305, United States.
² Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, United States.
³ SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, California 94025, United States.

PMID: 32786902
DOI: 10.1021/acs.jctc.0c00644

Abstract

The study of photoinduced dynamics in chemical systems necessitates accurate and computationally efficient electronic structure methods, especially as the systems of interest grow larger. The linear response hole-hole Tamm-Dancoff approximated (hh-TDA) density functional theory method was recently proposed to satisfy such demands. The N-electron electronic states are obtained by means of double annihilations on a doubly anionic (N + 2)-electron reference state, allowing for the ground and excited states to be formed on the same footing and thus enabling the correct description of conical intersections. Dynamic electron correlation effects are incorporated by means of the exchange-correlation functional. The accuracy afforded by the simultaneous treatment of static and dynamic correlation in addition to the relatively low computational cost, comparable to that of time-dependent density functional theory (TDDFT), makes it a promising ab initio electronic structure method for on-the-fly generation of potential energy surfaces in nonadiabatic dynamics simulations of photochemical systems, particularly those for which the nπ* and ππ* electronic excitations are most relevant. Here, we apply the hh-TDA method to nonadiabatic dynamics simulations of prototypical photochemical processes. First, we demonstrate the ability of hh-TDA to adequately describe conical intersection geometries. We next examine its ability to describe the ultrafast excited state dynamics of photoexcited ethylene through an ab initio multiple spawning (AIMS) dynamics simulation. Finally, we present an alternative variant of the hh-TDA method, which uses orbitals from a fractional occupation number Kohn-Sham (FON-KS) calculation applied to an ensemble with N-electrons. The resulting method is termed floating occupation molecular orbital hh-TDA (FOMO-hh-TDA). This scheme allows us to combine hh-TDA with global hybrid functionals and allows us to avoid unbound valence orbitals that may result from an (N + 2)-electron self-consistent field (SCF) procedure. FOMO-hh-TDA-BHLYP faithfully reproduces the nonadiabatic dynamics of trans-azobenzene (TAB) and is used to characterize the excited state decay pathways from the first (nπ*) excited state.