Ab initio molecular dynamics and time-resolved photoelectron spectroscopy of electronically excited uracil and thymine.
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 S2 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 S2/S1 conical intersection is responsible for the picosecond decay.
Department of Chemistry, Beckman Institute, and Center for Biophysics and Computational Biology, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
Hanneli R
HR
Hudock
Benjamin G
BG
Levine
Alexis L
AL
Thompson
Helmut
H
Satzger
D
D
Townsend
N
N
Gador
S
S
Ullrich
Albert
A
Stolow
Todd J
TJ
Martínez
D000465:Algorithms; D004583:Electrons; D010777:Photochemistry; D011789:Quantum Theory; D013057:Spectrum Analysis; D013941:Thymine / Q000737:chemistry* / Q000528:radiation effects; D013997:Time Factors; D014498:Uracil / Q000737:chemistry* / Q000528:radiation effects
D014498:Uracil; D013941:Thymine