title: Quantum vibrational analysis of hydrated ions using an ab initio potential.
abstract: We present full-dimensional potential energy surfaces (PESs) for hydrated chloride based on the sum of ab initio (H(2)O)Cl(-), (H(2)O)(2), and (H(2)O)(3) potentials. The PESs are shown to predict minima and corresponding harmonic frequencies accurately on the basis of comparisons with previous and new ab initio calculations for (H(2)O)(2)Cl(-), (H(2)O)(3)Cl(-), and (H(2)O)(4)Cl(-). An estimate of the effect of the 3-body water interaction is made using a simple 3-body water potential that was recently fit to tens of thousands of ab initio 3-body energies. Anharmonic, coupled vibrational calculations are presented for these clusters, using the "local monomer model" for the high frequency intramolecular modes. This model is tested against previous "exact" calculations for (H(2)O)Cl(-). Radial distribution functions at 0 K obtained from quantum zero-point wave functions are also presented for the (H(2)O)(2)Cl(-) and (H(2)O)(3)Cl(-) clusters.
authors.affiliation: Department of Chemistry, University of Southern California, Los Angeles, California 90089-0482, USA.
authors.forename: Eugene
authors.initials: E
authors.lastname: Kamarchik
authors.forename: Joel M
authors.initials: JM
authors.lastname: Bowman
mesh_terms: D002712:Chlorides / Q000737:chemistry; D006860:Hydrogen Bonding; D007477:Ions / Q000737:chemistry; D011789:Quantum Theory; D014732:Vibration; D014867:Water / Q000737:chemistry
chemical_list: D002712:Chlorides; D007477:Ions; D014867:Water