Electronically excited water aggregates and the adiabatic band gap of water

The authors report results for the electronic properties of the S(1) singlet excited state of H(3)O(+)[OH(H(2)O)((n-2))](-) aggregates, where n=2-5 is the number of water molecules. The energy of the excited state was defined relative to the ground state of neutral water clusters. Results for ionized aggregates are also reported. The results are based on configuration interaction with single excitations geometry optimizations followed by density functional theory and time dependent density functional theory calculations. Emphasis was placed on the relationship between electronic properties of the aggregates and the adiabatic band gap of liquid water. The authors' predictions for the adiabatic energy gap of water clusters are in the 6.01-6.55 eV range. These values are approximately 0.9-0.4 eV below the experimental adiabatic band gap of liquid water (6.9 eV). Comparison with experimental information for water is reported for several properties of interest including vertical and adiabatic ionization energies, excitation energies, photoemission thresholds, and conduction band edge. The results provide a description, at the molecular level, for the electronic properties of water aggregates that is consistent with the current picture for the band gap of bulk water [J. V. Coe, Int. Rev. Phys. Chem. 20, 33 (2001)].