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Functional and Basis Set Dependence for Time‐Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis ‐Azobenzene Photoisomerization
Author(s) -
Ye Linfeng,
Xu Chao,
Gu Feng Long,
Zhu Chaoyuan
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26116
Subject(s) - surface hopping , conical intersection , time dependent density functional theory , photoisomerization , density functional theory , basis set , excited state , molecular dynamics , azobenzene , basis (linear algebra) , diabatic , chemistry , computational chemistry , molecular physics , physics , quantum mechanics , molecule , isomerization , mathematics , adiabatic process , biochemistry , geometry , catalysis
Within three functionals (TD‐B3LYP, TD‐BHandHLYP, and TD‐CAM‐B3LYP) in combination with four basis sets (3‐21g, 6‐31g, 6‐31g(d), and cc‐pvdz), global switching (GS) trajectory surface hopping molecular dynamics has been performed for cis ‐to‐ trans azobenzene photoisomerization up to the S 1 (nπ*) excitation. Although all the combinations show artificial double‐cone structure of conical intersection between ground and first excited states, simulated quantum yields and lifetimes are in good agreement with one another; 0.6 (±5%) and 40.5 fs (±10%) by TD‐B3LYP, 0.5 (±10%) and 35.5 fs (±4%) by TD‐BHandHLYP, and 0.44 (±9%) and 35.2 fs (±10%) by TD‐CAM‐B3LYP. By analyzing distributions of excited‐state population decays, hopping spots, and typical trajectories with performance of 12 functional/basis set combinations, it has been concluded that functional dependence for given basis set is slightly more sensitive than basis set dependence for given functional. The present GS on‐the‐fly time‐dependent density functional theory (TDDFT) trajectory surface hopping simulation can provide practical benchmark guidelines for conical intersection driven excited‐state molecular dynamics simulation involving in large complex system within ordinary TDDFT framework. © 2019 Wiley Periodicals, Inc.