Theoretical investigations of spectroscopy and excited state dynamics of adenine

A set of harmonic potential surfaces have been obtained at the CASSCF/6-311 +G** level for the ground, n-pi*, and pi-pi* states of 9H-adenine. They have been used to analyze experimental R2PI and resonance fluorescence spectra and the excited state lifetimes of adenine. A tentative plausible assignment has been proposed, which takes into account a strong coupling between these electronic states. Using the potential surfaces, the excess energy dependence of the excited state lifetimes of adenine has been interpreted, and the lifetime of the n-pi* state at the band origin has also been estimated to be in the order of 10 ns. (C) 2007 Elsevier B.V. All rights reserved.