title: Insights into the ultraviolet spectrum of liquid water from model calculations: the different roles of donor and acceptor hydrogen bonds in water pentamers.
abstract: With a view toward a better understanding of changes in the peak position and shape of the first absorption band of water with condensation or temperature, results from electronic structure calculations using high level wavefunction based and time-dependent density functional methods are reported for water pentamers. Excitation energies, oscillator strengths, and redistributions of electron density are determined for the quasitetrahedral water pentamer in its C(2v) equilibrium geometry and for many pentamer configurations sampled from molecular simulation of liquid water. Excitations associated with surface molecules are removed in order to focus on those states associated with the central molecule, which are the most representative of the liquid environment. The effect of hydrogen bonding on the lowest excited state associated with the central molecule is studied by adding acceptor or donor hydrogen bonds to tetramer and trimer substructures of the C(2v) pentamer, and by sampling liquid-like configurations having increasing number of acceptor or donor hydrogen bonds of the central molecule. Our results provide clear evidence that the blueshift of excitation energies upon condensation is essentially determined by acceptor hydrogen bonds, and the magnitudes of these shifts are determined by the number of such, whereas donor hydrogen bonds do not induce significant shifts in excitation energies. This qualitatively different role of donor and acceptor hydrogen bonds is understood in terms of the different roles of the 1b(1) monomer molecular orbitals, which establishes an intimate connection between the valence hole and excitation energy shifts. Since the valence hole of the lowest excitation associated with the central molecule is found to be well localized in all liquid-like hydrogen bonding environments, with an average radius of gyration of ~1.6 Å that is much lower than the nearest neighbor O-O distance, a clear and unambiguous connection between hydrogen bonding environments and excitation energy shifts can be established. Based on these results, it is concluded that peak position of the first absorption band is mainly determined by the relative distribution of single and double acceptor hydrogen bonding environments, whereas the shape of the first absorption band is mainly determined by the relative distribution of acceptor and broken acceptor hydrogen bonding environments. The temperature dependence of the peak position and shape of the first absorption band can be readily understood in terms of changes to these relative populations.
authors.affiliation: Notre Dame Radiation Laboratory, University of Notre Dame, Notre Dame, Indiana 46556, USA.
authors.forename: Paulo
authors.initials: P
authors.lastname: Cabral do Couto
authors.forename: Daniel M
authors.initials: DM
authors.lastname: Chipman