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arXiv · 0806.4913

A full-dimensional quantum dynamical study of the vibrational ground state of $H_3O_2^-$ and its isotopomers

Yonggang Yang·Oliver Kühn
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Abstract

We investigated the effect of deuteration on 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 H/D isotope effect on the O--O distance which amounts to an elongation of about 0.005 A for the symmetric isotopomers and 0.009 A in the asymmetric case. Finally, we explore the isotopomer sensitivity of the ground state tunneling splitting due to the torsional motion of the two OH groups.

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Yonggang Yang, Oliver Kühn. 2008-06-30. A full-dimensional quantum dynamical study of the vibrational ground state of $H_3O_2^-$ and its isotopomers. https://doi.org/10.1524/zpch.2008.5396

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