Quantum chemical calculations of multidimensional dynamics probed in resonant inelastic X-ray scattering

Sammanfattning: This thesis is devoted to the theoretical study of the dynamical processes induced by light-matter interactions in molecules and molecular systems. To this end, the multidimensional nuclear dynamics probed in resonant inelastic X-ray scattering (RIXS) of small molecules, exemplified by H2O (g) and H2S (g), as well as more complex molecular systems, exemplified by NH3 (aq) and kaolinite clay, are modelled. The computational methodology consists of a combination of ab initio quantum chemistry calculations, quantum nuclear wave packet dynamics and in certain cases molecular dynamics modelling. This approach is used to simulate K-edge RIXS spectra and the theoretical results are evaluated against experimental measurements.Specifically, the vibrational profile for decay back to the electronic ground state of the H2O molecule displays a vibrational selectivity introduced by the dynamics in the core-excited state. Simulation of the inelastic decay channel to the electronic |1b1-1,4a11> valence-excited state shows that the splitting of the spectral profile arises from the contribution of decay in the OH fragment. The character of the S1s-1 and S2p-1 core-excited states of the H2S molecule has been investigated and distinct similarities and differences with the H2O molecule have been identified. RIXS has also been used as a probe of the hydrogen bonding environment in aqueous ammonia and by detailed analysis of the valence orbitals of NH3 and water, the spectral profiles are explained. Finally, it is shown that vibrations of weakly hydrogen bonding OH are excited in RIXS decay to the electronic ground state in kaolinite.