Physics
Scientific paper
Jun 2010
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2010mss..confemg12r&link_type=abstract
"International Symposium On Molecular Spectroscopy, 65th Meeting, Held 21-25 June, 2010 at Ohio State University. http://molspec
Physics
Electronic (Uv/Vis/Nir)
Scientific paper
The excited state dynamics of 9-methylpurine (9MP) were studied with broadband transient absorption spectroscopy in the time regime from femtoseconds to 3 nanoseconds. Excitation of 9MP in aqueous solutions at 266 nm results in ultrafast internal conversion from the initially excited S_2(ππ^ast) state to the S_1 state. Quantum chemical calculations that include bulk and explicit solvent interactions show that the S_1 state has significant nπ^ast character. Population of the S_1 state is followed by intersystem crossing (ISC) to the T_1(ππ^ast) state on a time scale of hundreds of picoseconds. Vanishingly small fluorescence yields were measured, supporting the dark character of the S_1 state as well as the high triplet yield in 9MP. Analogous experiments in acetonitrile show a decrease in the ISC lifetime by almost 50 % but an equally high triplet yield. The results presented in this work demonstrate the important role that the dark singlet state has in modulating the excited-state dynamics of DNA monomers in solution.
Crespo-Hernández Carlos E.
Reichardt Christian
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