A Full-Dimensional Quantum Dynamical Study of the Vibrational Ground State of H(3)O(2)(-) and its Isotopomers

作者：Yang Yonggang; Kuehn Oliver

来源：Zeitschrift fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics, 2008, 222(8-9): 1375-1387.

DOI：10.1524/zpch.2008.5396

• Strong H-Bonds
• Zero-Point Energy
• Geometric Isotope Effect
• Quantum Dynamics

We investigated the effect of deuteration oil the vibrational ground,state of the hydrated hydroxide anion using a nine-dimensional quantum dynamical model for the case of J = 0. The propagation of the nuclear wave function has been performed With the multi-configuration time-dependent Hartree method which yielded zero-point energies for the normal and fully deuterated species in quantitative agreement with previous diffusion Monte Carlo calculations, According to the zero-point energy the isotopomers having the hydrogen atom in the bridging position are more stable by about 1 kJ/mol as compared to the deuterium case. This holds irrespective of the deuteration state of the two OH groups. We also report the secondary geometric isotope effect on the O-O distance upon replacing the H- by a D-bond. It amounts to a contraction by about 0.005 angstrom for the symmetric isotopomers and 0.009 angstrom in the asymmetric case.

• 出版日期2008