A study of the valence photoelectron spectrum of uracil and mixed water-uracil clusters

International audienceThe valence ionization of uracil and mixed water-uracil clusters has been studied experimentally and by ab initio calculations. In both measurements the spectrum onset shows a red shift with respect to uracil molecule, with the mixed cluster characterized by peculiar features unexplained by the sum of independent contributions of the water or uracil aggregation. To interpret and assign all the contributions, we performed a series of multi-level calculations, starting from an exploration of several cluster structures using automated conformer-search algorithms based on a tight-binding approach. Ionization energies have been assessed on smaller clusters via a comparison between accurate wavefunction-based approaches and cost-effective DFT-based simulations, the latter applied to clusters up to twelve uracil and thirty-six water molecules. The results confirm that i) the bottom-up approach based on a multilevel method (Mattioli et al. PCCP 23, 2021, 1859) to the structure of neutral clusters of unknown experimental composition converges to precise structure-property relationships and ii) the coexistence of pure and mixed clusters in the wateruracil samples. A natural bond orbital (NBO) analysis performed on a subset of clusters highlighted the special role of H-bonds in the formation of the aggregates. The NBO analysis yields a second-order perturbative energy between H-bond donor and acceptor orbitals correlated with the calculated ionization energies. This sheds light on the role of the oxygen lone-pairs of the uracil CO group in the formation of strong H-bonds, with a stronger directionality in mixed clusters, giving quantitative explanation for the formation of core-shell structures