Gas phase PES spectrum of water taken from Ref. 25 measured at a photon energy of and PES spectra of ice at photon energies of and . The bottom theoretical spectra are described in detail in the text.
XAS spectra of gas phase water from Ref. 27 and ice together with a DFT calculation of hexagonal ice described with a 44-molecule cluster. The spectral feature in the ice XAS spectrum at is connected to broken H-bonds at the ice surface, (Refs. 28 and 35).
Computed XES (PES component) spectra of the central molecule in a 44-molecule ice cluster. Each individual component is separately displayed and labeled according to the orbital symmetry of the free water molecule. The contributions were obtained from a computed spectrum using an transition operator.
Computed XAS spectra for the central molecule in a 44-molecule ice cluster. Each individual component is separately displayed and labeled according to the orbital symmetry of the free water molecule. The contributions were obtained from a computed spectrum using an transition operator.
(Color) Charge density difference (CDD) plots for a cluster where the two central water molecules are in a local tetrahedral configurations. (a) The configuration consists of two water molecules in the center in acceptor and donor positions, each fully coordinated with three additional molecules in a tetrahedral arrangement. (b) CDD between frozen orbital and fully relaxed orbital configurations, and (c) frozen orbital and partly relaxed to allow polarization on individual waters.
Computed XES spectra (representing contributions to PES) and energetics of interaction from various stages of the CSOV analysis of a water pentamer in a tetrahedral bonding configuration. Note that the change in the relaxed spectrum compared to the spectrum in Fig. 3 is due to the difference in number of water molecules in the cluster. The splitting in can be seen at 8 and binding energies.
Oxygen charge occupancy (electrons) of particular atomic orbital symmetry in different water MOs obtained through integration of the spectra in Fig. 3. The absolute contribution was normalized to a occupancy for the lone pair orbital in a free water molecule and the contribution was normalized with the aid of a spectrum of a free oxygen atom with atomic configuration where the total content is equal to a occupancy.
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