Acetone–water complexes at MRCI level using localized orbitals: n → π∗ and π → π∗ electronic transitions

The n → π∗ and π → π∗ vertical electronic transitions of acetone with two and four H2O which correspond to a first solvation shell are considered. By using localized orbitals, and thanks to the MRCI approach which permits to know the wave function, the role of the various solvent molecules is analysed in details. Distinguishing the solvent molecules allows one to consider them at different calculation levels. The methodology is to compare the spectra obtained with four H2O, with two H2O either in the acetone plane or in a perpendicular plane and when they are completely or partly frozen.