The degree of initial hole localization/delocalization in ionized water clusters

P.A. Pieniazek, E.J. Sundstrom, S.E. Bradforth, and A.I. Krylov
J. Phys. Chem. A 113, 4423 – 4429 (2009)

The electronic structure of ionized bulk liquid water presents a number of theoretical challenges. Not the least of these is the realization that the detailed geometry of the hydrogen bonding network is expected to have a strong effect on the electronic couplings between water molecules and thus the degree of delocalization of the initially ionized system. This problem is approached from a cluster perspective where a high-level coupled cluster description of the electronic structure is still possible. Building on work and methodology developed for the water dimer cation [J. Phys. Chem. A 112, 6159 (2008)], the character and spectrum of electronic states of the water hole and their evolution from the dimer into higher clusters is presented. As the time evolution of the initially formed hole can in principle be followed by the system's transient absorption spectrum, the state spacing and transition strengths are computed. An analysis involving Dyson orbitals is applied and shows a partially delocalized nature of states. The issue of conformation disorder in the hydrogen bonding geometry is addressed for the water dimer cation.

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