Ab initio implementation of quantum trajectory mean-field approach and dynamical simulation of the N2CO photodissociation

作者：Xie, Binbin; Liu, Lihong; Cui, Ganglong; Fang, Wei-Hai^*; Cao, Jun; Feng, Wei; Li, Xin-qi

来源：Journal of Chemical Physics, 2015, 143(19): 194107.

DOI：10.1063/1.4935800

• GREEN FLUORESCENT PROTEIN
• PROTON-TRANSFER REACTIONS
• HYDROGEN-BONDED PHENOLS
• MOLECULAR-DYNAMICS
• ELECTRONIC-TRANSITIONS
• NONADIABATIC DYNAMICS
• EXCITON FISSION
• CHARGE-TRANSFER
• DIAZIRINONE
• COLLISIONS

In this work, the recently introduced quantum trajectory mean-field (QTMF) approach is implemented and employed to explore photodissociation dynamics of diazirinone (N2CO), which are based on the high-level ab initio calculation. For comparison, the photodissociation process has been simulated as well with the fewest-switches surface hopping (FSSH) and the ab initio multiple spawning (AIMS) methods. Overall, the dynamical behavior predicted by the three methods is consistent. The N2CO photodissociation at lambda > 335 nm is an ultrafast process and the two C-N bonds are broken in a stepwise way, giving birth to CO and N-2 as the final products in the ground state. Meanwhile, some noticeable differences were found in the QTMF, FSSH, and AIMS simulated time constants for fission of the C-N bonds, excited-state lifetime, and nonadiabatic transition ratios in different intersection regions. These have been discussed in detail. The present study provides a clear evidence that direct ab initio QTMF approach is one of the reliable tools for simulating nonadiabatic dynamics processes.

• 出版日期2015-11-21
• 单位北京师范大学; 贵州师范学院