RESUMO
The impact of the solvent on the photodissociation of embedded molecules has been intensively investigated in the last decades. Collisions of photofragments with the solvating atoms or molecules can change their kinetic energy distribution or even lead to the de-excitation of the dissociating molecule to a bound electronic state quenching the dissociation. In this article we show that this cage effect is strongly enhanced if interatomic Coulombic decay (ICD) of the excited state becomes allowed. Ab initio calculations in H2O-Cl(-) cluster show that the ultra-fast dissociation of water in the à excited state is strongly quenched by ICD. We found that this very efficient quenching is due to two factors. First, the lifetimes of the à state due to ICD are short ranging between 6 and 30 fs. Second, nuclear dynamics is dominated by the chattering motion of the H atom between O and Cl(-) allowing ICD to act for longer times. We hope that this work will be an important first step in clarifying the impact of ICD on photodissociation of embedded molecules.
RESUMO
The X-ray absorption spectra (XAS) of Ar2 and ArNe dimers and small Ar clusters in the L2,3 region (244-252 eV) of the Ar atom have been recorded using synchrotron light and a combination of coincidence methods and kinetic energy discrimination of energetic ions. The absorption peaks in the spectra of the dimers and clusters were found to be shifted and broadened relative to the peaks in the spectrum of the Ar atom. In order to unambiguously relate these chemical shifts to the electronic structure of the core excited states in dimers, we performed ab initio calculations of the XAS spectra. Implications of the results for the use of XAS as a structure determination method in large rare gas clusters are discussed.
