Nonadiabatic Tunneling in Photodissociation of Phenol.
Using recently developed full-dimensional coupled quasi-diabatic ab initio potential energy surfaces including four electronic ((1)ππ, (1)ππ*, 1(1)πσ*, and 2(1)πσ*) states, the tunneling dynamics of phenol photodissociation via its first excited singlet state (S1 ← S0) is investigated quantum mechanically using a three-dimensional model. The lifetimes of several low-lying vibrational states are examined and compared with experiment. The deuteration of the phenoxyl hydrogen is found to dramatically increase the lifetime, attesting to the tunneling nature of the nonadiabatic dissociation. Importantly, it is shown that owing to the conical intersection topography tunneling in this system cannot be described in the standard adiabatic approximation, which eschews the geometric phase effect since the nonadiabatically computed lifetimes, validated by comparison with experiment, differ significantly from those obtained in that limit.
Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.|Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, China.
Changjian
C
Xie
Institute of Atomic and Molecular Physics, Sichuan University , Chengdu, Sichuan 610065, China.
Jianyi
J
Ma
Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.
Xiaolei
X
Zhu
Department of Chemistry, Johns Hopkins University , Baltimore, Maryland 21218, United States.
David R
DR
Yarkony
Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, China.|Synergetic Innovation Center of Quantum Information and Quantum Physics, University of Science and Technology of China, Hefei , Anhui 230026, China.
Daiqian
D
Xie
Department of Chemistry and Chemical Biology, University of New Mexico , Albuquerque, New Mexico 87131, United States.
Hua
H
Guo