Insights into the ultraviolet spectrum of liquid water from model calculations: the different roles of donor and acceptor hydrogen bonds in water pentamers.

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.

Insights into the ultraviolet spectrum of liquid water from model calculations.

With a view toward a better molecular level understanding of the effects of hydrogen bonding on the ultraviolet absorption spectrum of liquid water, benchmark electronic structure calculations using high level wave function based methods and systematically enlarged basis sets are reported for excitation energies and oscillator strengths of valence excited states in the equilibrium water monomer and dimer and in a selection of liquid-like dimer structures. Analysis of the electron density redistribution associated with the two lowest valence excitations of the water dimer shows that these are usually localized on one or the other monomer, although valence hole delocalization can occur for certain relative orientations of the water molecules. The lowest excited state is mostly associated with the hydrogen bond donor and the significantly higher energy second excited state mostly with the acceptor. The magnitude of the lowest excitation energies is strongly dependent on where the valence hole is created, and only to a lesser degree on the perturbation of the excited electron density distribution by the neighboring water molecule. These results suggest that the lowest excitation energies in clusters and liquid water can be associated with broken acceptor hydrogen bonds, which provide energetically favorable locations for the formation of a valence hole. Higher valence excited states of the dimer typically involve delocalization of the valence hole and/or delocalization of the excited electron and/or charge transfer. Two of the higher valence excited states that involve delocalized valence holes always have particularly large oscillator strengths. Due to the pervasive delocalization and charge transfer, it is suggested that most condensed phase water valence excitations intimately involve more than one water molecule and, as a consequence, will not be adequately described by models based on perturbation of free water monomer states. The benchmark calculations are further used to evaluate a series of representative semilocal, global hybrid, and range separated hybrid functionals used in efficient time-dependent density functional methods. It is shown that such an evaluation is only meaningful when comparison is made at or near the complete basis set limit of the wave function based reference method. A functional is found that quantitatively describes the two lowest excitations of water dimer and also provides a semiquantitative description of the higher energy valence excited states. This functional is recommended for use in further studies on the absorption spectrum of large water clusters and of condensed phase water.

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)].