Quantum-mechanical probabilistic structure of the water dimer with an excess electron

Abstract

Weakly dipole-bound electron systems having large wide-ranging zero vibrational effects often exhibit large discrepancies between theory and experiment. The present study utilizing a quantum-mechanical probabilistic approach characterizes the structure of the anionic water dimer $[e+({\mathrm{H}}_{2}\mathrm{O}{)}_{2}]$ (one of the most weakly dipole-bound electron systems) as linearlike, slightly towards the cis conformer at 0 K. The resulting electron detachment energy, adiabatic electron affinity, and the deuteration effect of the predicted structure are in good agreement with experimental results.