Transient X-ray Absorption Spectral Fingerprints of the S1 Dark State in Uracil

Low-lying dark n pi* states play an important role in many photophysical and photochemical processes of organic chromophores. Transient X-ray absorption spectroscopy (TXAS) provides a powerful technique for probing the dynamics of valence states by exciting the electrons into high-lying core excited states. We employ multiconfigurational self-consistent field calculations to investigate the TXAS of uracil along its nonradiative photodecay pathways. An open issue is whether dark n pi* state S-1 (n is the lone pair localized on an oxygen atom) is accessible when bright n pi* state S-2 is selectively excited. Vertical core excitations were calculated along the potential energy surfaces of the three lowest states, S-0-S-2, interpolated between two minima and two minimum-energy conical intersections. Computed TXAS data from the C, N, and O K edges show distinct spectral fingerprints of the dark state in all spectral regimes. At the O is edge, the n pi* state has a very strong absorption at 526-527 eV, while at the C (N) is edge, by contrast, there is almost zero (very weak) absorption at 279-282 eV (397-398 eV). All K-edge spectra can be used to sensitively detect the dark states. Our proposed O 1s feature has already been observed in a recent TXAS experiment with thymine. Natural transition orbital analysis is used to interpret all dominant features of the three lowest-valence states along the reaction coordinate and reveal some important valence fine-structure information from the core excitation.