title: Theoretical study of the ground and excited states of 7-methyl guanine and 9-methyl guanine: comparison with experiment.
abstract: The keto-enol tautomerization of 7-methyl-guanine and 9-methyl-guanine in the excited state was investigated using the time-dependent DFT (TDDFT) method. For both species, the potential energy surfaces of the ground state and two lowest singlet excited states (due to pi-->pi* and n-->pi* transitions) have been investigated and their features discussed in terms of consequences on the excited state dynamics. The findings suggest that, for both species, the state due to the n-->pi* transition, suspected to be an intermediate in the excited state deactivation, exhibits two minima with the second minimum characterized by an elongated N1-H distance. This structure, intermediate between enol and keto tautomers, might play a role in the excited state relaxation. The existence of this second well, however, is observed in both 7- and 9-methyl-guanine, which suggests that it cannot account alone for the different photophysical behavior of these species.
authors.affiliation: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, 166 10, Prague 6, Czech Republic.
authors.forename: Jirí
authors.initials: J
authors.lastname: Cerný
authors.forename: Vladimír
authors.initials: V
authors.lastname: Spirko
authors.forename: Michel
authors.initials: M
authors.lastname: Mons
authors.forename: Pavel
authors.initials: P
authors.lastname: Hobza
authors.forename: Dana
authors.initials: D
authors.lastname: Nachtigallová
mesh_terms: D003198:Computer Simulation; D006147:Guanine / Q000031:analogs & derivatives* / Q000737:chemistry; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation
chemical_list: C116701:9-methylguanine; D006147:Guanine; C008450:7-methylguanine