The density of states and band gap of liquid water by sequential Monte Carlo/Quantum mechanics calculations

Electronic properties of liquid water were investigated by sequential Monte Carlo/Quantum mechanics calculations. The density of states (DOS) and HOMO-LUMO gap (E G) of liquid water have been determined by Hartree-Fock and Density Functional Theory (DFT) calculations. The quantum mechanical calculations were carried out over uncorrelated supermolecular structures generated by the Monte Carlo simulations. The DFT calculations were performed with a modified B3LYP exchange-correlation functional proposed by Abu-Awwad and Politzer which was parametrized to reproduce valence orbital energies in agreement with experimental ionization potentials of the water molecule. We have analyzed the dependence of the DOS and HOMO-LUMO gap on the number of water molecules and on surface effects. Our prediction for E G is 6:5 ± 0:5 eV in good agreement with a recent experimental prediction of 6.9 eV