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Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization.

Abstract

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 S1 (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.

Authors+Show Affiliations

Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment of South China Normal University, Guangzhou, 51006, People's Republic of China.Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment of South China Normal University, Guangzhou, 51006, People's Republic of China.Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment of South China Normal University, Guangzhou, 51006, People's Republic of China.Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment of South China Normal University, Guangzhou, 51006, People's Republic of China. Institute of Molecular Science and Department of Applied Chemistry, National Chiao Tung University, Hsinchu, 30010, Taiwan. Key Center for Emergent Functional Matter Science, National Chiao Tung University, Hsinchu, 30010, Taiwan.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

31743473

Citation

Ye, Linfeng, et al. "Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization." Journal of Computational Chemistry, 2019.
Ye L, Xu C, Gu FL, et al. Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization. J Comput Chem. 2019.
Ye, L., Xu, C., Gu, F. L., & Zhu, C. (2019). Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization. Journal of Computational Chemistry, doi:10.1002/jcc.26116.
Ye L, et al. Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization. J Comput Chem. 2019 Nov 19; PubMed PMID: 31743473.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Functional and Basis Set Dependence for Time-Dependent Density Functional Theory Trajectory Surface Hopping Molecular Dynamics: Cis-Azobenzene Photoisomerization. AU - Ye,Linfeng, AU - Xu,Chao, AU - Gu,Feng Long, AU - Zhu,Chaoyuan, Y1 - 2019/11/19/ PY - 2019/09/11/received PY - 2019/10/26/revised PY - 2019/11/04/accepted PY - 2019/11/20/entrez PY - 2019/11/20/pubmed PY - 2019/11/20/medline KW - conical intersections KW - global switching KW - molecular dynamics simulation KW - on-the-fly trajectory surface hopping KW - photoisomerization KW - time-dependent density functional theory JF - Journal of computational chemistry JO - J Comput Chem N2 - 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 S1 (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. SN - 1096-987X UR - https://www.unboundmedicine.com/medline/citation/31743473/Functional_and_Basis_Set_Dependence_for_Time-Dependent_Density_Functional_Theory_Trajectory_Surface_Hopping_Molecular_Dynamics:_Cis-Azobenzene_Photoisomerization L2 - https://doi.org/10.1002/jcc.26116 DB - PRIME DP - Unbound Medicine ER -