title: Benchmark Performance of Global Switching versus Local Switching for Trajectory Surface Hopping Molecular Dynamics Simulation: Cis↔Trans Azobenzene Photoisomerization.
abstract: A newly developed global switching algorithm that does not require calculation of nonadiabatic coupling vectors reduces computational costs significantly. However, the accuracy of this simplest nonadiabatic molecular dynamic method has not been extensively compared with the conventional Tully's fewest switches. It is necessary to demonstrate the accuracy of this global switching algorithm. An extensive comparison between local and global switching on-the-fly trajectory surface hopping molecular dynamics is performed for cis-to-trans (800 sampling trajectories) and trans-to-cis (600 sampling trajectories) azobenzene photoisomerization at the OM2/MRCI level. The global switching algorithm is coded into the Newton-X program package. Excellent agreement between the two switching algorithms is obtained not only for highly averaged quantities of quantum yields and lifetimes, but also for detailed contour patterns of product distributions, hopping spot distributions and hopping directions in terms of conical intersections between ground and the first excited states. Therefore, the global switching trajectory surface hopping method can be applied to larger complex systems in which nonadiabatic coupling is not available for excited-state molecular dynamic simulations.
authors.affiliation: Institute of Molecular Science, Department of Applied Chemistry and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, 30010, Taiwan.|MOX Key Laboratory for Nonequilibrium, Synthesis and Modulation of Condensed Matter, State Key Laboratory for Mechanical Behavior of Materials and Institute of Chemistry for New Energy Materials, Department of Chemistry, Faculty of Science, Xi'an Jiaotong University, Xi'an, 710049, P. R. China.
authors.forename: Ling
authors.initials: L
authors.lastname: Yue
authors.affiliation: Institute of Molecular Science, Department of Applied Chemistry and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, 30010, Taiwan.|Key Laboratory of Synthetic and Natural, Functional Molecule Chemistry of Ministry of Education, The College of Chemistry & Materials Science, Shaanxi key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an, 710069, P. R. China.
authors.forename: Le
authors.initials: L
authors.lastname: Yu
authors.affiliation: Institute of Molecular Science, Department of Applied Chemistry and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, 30010, Taiwan.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631, P. R. China.
authors.forename: Chao
authors.initials: C
authors.lastname: Xu
authors.affiliation: Key Laboratory of Synthetic and Natural, Functional Molecule Chemistry of Ministry of Education, The College of Chemistry & Materials Science, Shaanxi key Laboratory of Physico-Inorganic Chemistry, Northwest University, Xi'an, 710069, P. R. China.
authors.forename: Yibo
authors.initials: Y
authors.lastname: Lei
authors.affiliation: Laboratory of Theoretical and Computational Photochemistry, Ministry of Education, College of Chemistry, Beijing Normal University, Beijing, 100875, P. R. China.
authors.forename: Yajun
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Institute of Molecular Science, Department of Applied Chemistry and Center for Interdisciplinary Molecular Science, National Chiao Tung University, Hsinchu, 30010, Taiwan.|Center for Computational Quantum Chemistry, South China Normal University, Guangzhou, 510631, P. R. China.
authors.forename: Chaoyuan
authors.identifier: http://orcid.org/0000-0003-3959-6705
authors.initials: C
authors.lastname: Zhu
keywords: conical intersections; molecular dynamics; nonadiabatic transitions; on-the-fly trajectory surface hopping; photoisomerization