Excited-state dynamics of cytosine tautomers.

We report the relaxation dynamics of keto and enol or keto-imino cytosine, photoexcited in the wavelength range of 260-290 nm. Three transients with femtosecond to hundreds of picoseconds lifetimes are observed for the biologically relevant keto tautomer and are assigned to internal conversion and excited-state tautomerization. Only two transients with femtosecond and picosecond lifetimes are identified for the enol or keto-imino tautomer and are assigned to internal conversion processes. The results are discussed in the context of published ab initio theory.