Electronic structure of the water dimer cation

Abstract

The spectroscopic signatures of proton transfer in the water dimer cation were investigated. The six lowest electronic states were characterized along the reaction coordinate using the equation-of-motion coupled-Cluster with single and double substitutions method for ionized systems. The nature of the dimer states was explained in. terms of the monomer states using a qualitative molecular orbital framework. We found that proton transfer induces significant changes in the electronic spectrum, thus Suggesting that time-resolved electronic femtosecond spectroscopy is an effective strategy to monitor the dynamics following ionization. The electronic spectra at vertical and proton-transferred configurations include both local exitations (features C similar to those of the monomers) and charge-transfer bands. Ab initio calculations were used to test the performance of a self-interaction correction for density functional theory (DFT). The corrected DFT/BLYP method is capable of quantitatively reproducing the proper energetic ordering of the (H2O)(2)(+) isomers and thus is a reasonable approach for calculations of larger systems.