Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 112, Issue 47, Pages 11965-11968Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp806622m
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Funding
- Deutsche Forschungsgemeinschaft (DFG) [SFB 749]
- Alexander von Humboldt Foundation
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We present the excited-state potential energy profiles of the biologically relevant 9H-keto-amino tautomer of guanine with respect to the radiationless decay via the out-of-plane deformation of the six-membered ring as well as the dissociation of NH bonds. The CASPT2//CASSCF method is employed for the reaction-path calculations. The reaction path for the out-of-plane deformation in the (1)pi pi* state leads in a barrierless way to a conical intersection with the electronic ground state. For the NH dissociation via the (1)pi sigma* state, the 9H-keto-amino tautomer is shown to have lower energy barriers than the 7H tautomers which we have studied recently. These two radiationless decay mechanisms explain the unexpected missing of the biologically relevant form in the resonant two-photon ionization spectrum of guanine in a supersonic jet. It is suggested that these ultrafast deactivation processes provide the biologically relevant tautomer of guanine with a high degree of photostability.
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