CC BY 4.0 UnportedBuchner, FranziskaNakayama, AkiraYamazaki, ShoheiRitze, Hans-HermannLübcke, Andrea2022-07-012022-07-012015https://oa.tib.eu/renate/handle/123456789/9457https://doi.org/10.34657/8495Time-resolved photoelectron spectroscopy is performed on thymine and thymidine in aqueous solution to study the excited-state relaxation dynamics of these molecules. We find two contributions with sub-ps lifetimes in line with recent excited-state QM/MM molecular dynamics simulations (J. Chem. Phys.2013, 139, 214304). The temporal evolution of ionization energies for the excited ππ* state along the QM/MM molecular dynamics trajectories were calculated and are compatible with experimental results, where the two contributions correspond to the relaxation paths in the ππ* state involving different conical intersections with the ground state. Theoretical calculations also show that ionization from the nπ* state is possible at the given photon energies, but we have not found any experimental indication for signal from the nπ* state. In contrast to currently accepted relaxation mechanisms, we suggest that the nπ* state is not involved in the relaxation process of thymine in aqueous solution.enghttps://creativecommons.org/licenses/by/4.0/540Ground stateIonizationLiquidsMolecular dynamicsPhotoelectron spectroscopyPhotoelectronsPhotoionizationPhotonsRelaxation processesSolutionsConical intersectionExcited state relaxationMolecular dynamics simulationsMolecular dynamics trajectoriesRelaxation mechanismTemporal evolutionTheoretical calculationsTime-resolved photoelectron spectroscopyExcited statesthymidinethyminehydrogenthymidinethyminewaterab initio calculationaqueous solutionArticlecontrolled studyelectronexcitationhydrationionizationliquidmolecular dynamicsmolecular mechanicsphotonquantum mechanicssimulationstatic electricitytheoretical modeltimeX ray photoelectron spectroscopychemistryconformationHydrogenMolecular ConformationMolecular Dynamics SimulationPhotoelectron SpectroscopyThymidineThymineWaterArticle