A three-state model for the photophysics of guanine

被引:134
|
作者
Serrano-Andres, Luis [1 ]
Merchan, Manuela [1 ]
Borin, Antonio Carlos [2 ]
机构
[1] Univ Valencia, Inst Ciencia Mol, ES-46071 Valencia, Spain
[2] Univ Sao Paulo, Inst Quim, BR-05508900 Sao Paulo, Brazil
关键词
D O I
10.1021/ja0744450
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The nonadiabatic photochemistry of the guanine molecule (2-amino-6-oxopurine) and some of its tautomers has been studied by means of the high-level theoretical ab initio quantum chemistry methods CASSCF and CASPT2. Accurate computations, based by the first time on minimum energy reaction paths, states minima, transition states, reaction barriers, and conical intersections on the potential energy hypersurfaces of the molecules lead to interpret the photochemistry of guanine and derivatives within a three-state model. As in the other purine DNA nucleobase, adenine, the ultrafast subpicosecond fluorescence decay measured in guanine is attributed to the barrierless character of the path leading from the initially populated (1)(pi pi* L-a) spectroscopic state of the molecule toward the low-lying methanamine-like conical intersection (gs/pi pi* L-a)(CI). On the contrary, other tautomers are shown to have a reaction energy barrier along the main relaxation profile. A second, slower decay is attributed to a path involving switches toward two other states, (1)(pi pi* L-b) and, in particular, (1)(n(o)pi*), ultimately leading to conical intersections with the ground state. A common framework for the ultrafast relaxation of the natural nucleobases is obtained in which the predominant role of a pi pi*-type state is confirmed.
引用
收藏
页码:2473 / 2484
页数:12
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