REMPI spectroscopy of cytosine

We report resonant two-photon ionization spectra of laser desorbed, jet cooled, cytosine, 1-methyl cytosine, 5-methyl cytosine, and dimers of these. Unlike other pyrimidine bases, cytosine exhibits vibronic spectra with sharp features in two spectral regions, separated by about 5000 cm−1. We interpret these as being due to two tautomeric forms, one keto and one enol. The dimers absorb at wavelengths that are intermediate between those of the two monomer forms. By UV–UV hole burning we determined the numbers of isomers contributing to each spectrum and by delayed two color ionization we determined triplet lifetimes. We observed hydrogen transfer between bases both in collisions between monomers and after photo-excitation in clusters.