Cavity quantum-electrodynamical time-dependent density functional theory within Gaussian atomic basis. II. Analytic energy gradient

Junjie Yang; Zheng Pei; Erick Calderon Leon; Carly Wickizer; Binbin Weng; Yuezhi Mao; Qi Ou; Yihan Shao

doi:10.1063/5.0082386

Cavity quantum-electrodynamical time-dependent density functional theory within Gaussian atomic basis. II. Analytic energy gradient

J Chem Phys. 2022 Mar 28;156(12):124104. doi: 10.1063/5.0082386.

Authors

Junjie Yang¹, Zheng Pei², Erick Calderon Leon¹, Carly Wickizer¹, Binbin Weng³, Yuezhi Mao⁴, Qi Ou⁵, Yihan Shao¹

Affiliations

¹ Department of Chemistry and Biochemistry, University of Oklahoma, Norman, Oklahoma 73019, USA.
² State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, People's Republic of China.
³ Microfabrication Research and Education Center and School of Electrical and Computer Engineering, University of Oklahoma, Norman, Oklahoma 73019, USA.
⁴ Department of Chemistry, Stanford University, Stanford, California 94305, USA.
⁵ MOE Key Laboratory of Organic OptoElectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China.

PMID: 35364897
DOI: 10.1063/5.0082386

Abstract

Following the formulation of cavity quantum-electrodynamical time-dependent density functional theory (cQED-TDDFT) models [Flick et al., ACS Photonics 6, 2757-2778 (2019) and Yang et al., J. Chem. Phys. 155, 064107 (2021)], here, we report the derivation and implementation of the analytic energy gradient for polaritonic states of a single photochrome within the cQED-TDDFT models. Such gradient evaluation is also applicable to a complex of explicitly specified photochromes or, with proper scaling, a set of parallel-oriented, identical-geometry, and non-interacting molecules in the microcavity.