Ab initio molecular dynamics and time-resolved photoelectron spectroscopy of electronically excited uracil and thymine

作者：Hudock Hanneli R; Levine Benjamin G; Thompson Alexis L; Satzger Helmut; Townsend D; Gador N; Ullrich S; Stolow Albert; Martinez Todd J^*

来源：Journal of Physical Chemistry A, 2007, 111(34): 8500-8508.

DOI：10.1021/jp0723665

The reaction dynamics of excited electronic states in nucleic acid bases is a key process in DNA photodamage. Recent ultrafast spectroscopy experiments have shown multicomponent decays of excited uracil and thymine, tentatively assigned to nonadiabatic transitions involving multiple electronic states. Using both quantum chemistry and first principles quantum molecular dynamics methods we show that a true minimum on the bright S-2 electronic state is responsible for the first step that occurs on a femtosecond time scale. Thus the observed femtosecond decay does not correspond to surface crossing as previously thought. We suggest that subsequent barrier crossing to the minimal energy S-2/S-1 conical intersection is responsible for the picosecond decay.

• 出版日期2007-8-30