title: Intersystem crossing-branched excited-state intramolecular proton transfer for o-nitrophenol: An ab initio on-the-fly nonadiabatic molecular dynamic simulation.
abstract: The 6SA-CASSCF(10, 10)/6-31G (d, p) quantum chemistry method has been applied to perform on-the-fly trajectory surface hopping simulation with global switching algorithm and to explore excited-state intramolecular proton transfer reactions for the o-nitrophenol molecule within low-lying electronic singlet states (S0 and S1) and triplet states (T1 and T2). The decisive photoisomerization mechanisms of o-nitrophenol upon S1 excitation are found by three intersystem crossings and one conical intersection between two triplet states, in which T1 state plays an essential role. The present simulation shows branch ratios and timescales of three key processes via T1 state, non-hydrogen transfer with ratio 48% and timescale 300 fs, the tunneling hydrogen transfer with ratios 36% and timescale 10 ps, and the direct hydrogen transfer with ratios 13% and timescale 40 fs. The present simulated timescales might be close to low limit of the recent experiment results.
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China.
authors.forename: Chao
authors.initials: C
authors.lastname: Xu
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.|State Key Laboratory for Physical Chemistry of Solid Surfaces and Fujian Provincial Key Lab of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Chaoyuan
authors.initials: C
authors.lastname: Zhu
authors.affiliation: College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China.
authors.forename: Jianguo
authors.initials: J
authors.lastname: Yu
authors.affiliation: State Key Laboratory for Physical Chemistry of Solid Surfaces and Fujian Provincial Key Lab of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, P. R. China.
authors.forename: Zexing
authors.initials: Z
authors.lastname: Cao