A convenient set of vibrational coordinates for 2D calculation of the tunneling splittings of the ground state and some excited vibrational states for the inversion motion in H3O+, H3O-, and H3O.

Splitting of the ground state and some excited symmetric bending vibrational states due to inversion tunneling of the oxygen atom in the H3O+, H3O- ions and in the H3O radical are analyzed by numerically solving the vibrational Schrödinger equation of restricted (2D) dimensionality. As two vibrational coordinates, we used 1) the distance of the oxygen atom from the plane of a regular triangle formed by three hydrogen atoms and 2) a symmetry coordinate composed of three distances between chemically non-bonded hydrogen atoms. The kinetic energy operator in this case takes the simplest form. The 2D potential energy surface (PES) in the given coordinates was calculated for H3O+ at the CCSD(T)/aug-cc-pVTZ and CCSD(T)-F12/cc-pVTZ-F12 levels of theory. The same 2D PES for the H3O- anion and H3O radical were calculated at the CCSD(T)/aug-cc-pVQZ, CCSD(T)/d-aug-cc-pVQZ and UCCSD(T)/aug-cc-pVQZ, UCCSD(T)/d-aug-cc-pVQZ levels of theory, respectively. The tunneling splittings were calculated for the cations H316O+, D316O+, T316O+, H318O+, D318O+, T318O+. The tunneling splittings for the H3O-, D3O-, T3O- anions and H3O, D3O, T3O radicals were calculated for the first time. The results of calculations demonstrate good agreement with experimental values of the tunneling splittings in the ground state and in some excited vibrational states of the H316O+ and D316O+ cations.

A proposal for the structure of high- and low-density fluctuations in liquid water.

Based on recent experimental data that can be interpreted as indicating the presence of specific structures in liquid water, we build and optimize two structural models which we compare with the available experimental data. To represent the proposed high-density liquid structures, we use a model consisting of chains of water molecules, and for low-density liquid, we investigate fused dodecahedra as templates for tetrahedral fluctuations. The computed infrared spectra of the models are in very good agreement with the extracted experimental spectra for the two components, while the extracted structures from molecular dynamics (MD) simulations give spectra that are intermediate between the experimentally derived spectra. Computed x-ray absorption and emission spectra as well as the O-O radial distribution functions of the proposed structures are not contradicted by experiment. The stability of the proposed dodecahedral template structures is investigated in MD simulations by seeding the starting structure, and remnants found to persist on an ∼30 ps time scale. We discuss the possible significance of such seeds in simulations and whether they can be viable candidates as templates for structural fluctuations below the compressibility minimum of liquid water.