TY - JOUR

T1 - Isotope effects in hydrogen-bonded complexes. Calculation of geometrical and vibrational characteristics of asymmetric isotopologues of [F(HF)2]-

AU - Bulychev, V.P.

AU - Buturlimova, M.V.

AU - Tokhadze, K.G.

PY - 2011

Y1 - 2011

N2 - The geometrical and vibrational characteristics of isolated H-bonded anionic complexes [FHFDF]−, [FHFTF]−, and [FDFTF]− are calculated quantum-mechanically. The four-dimensional anharmonic vibrational problems are solved by the variational method using the potential energy and dipole moment surfaces calculated in the MP2/6-311++G(3df,3pd) approximation with the basis set superposition error taken into account. Changes in the bond lengths of molecular fragments LF (L = H, D, T) and in the distances between the F− anion and the centers of mass of LF are used as the vibrational coordinates. For each isotopologue, the vibrational energy levels, the transition frequencies and absolute intensities for the H-bond and L–F stretching vibrations are determined. To study the isotope effects on the geometrical parameters, the values of internuclear separations and the asymmetry parameter of the F−L–F bridges, averaged over the ground state and several excited vibrational states, are calculated, as well as their standard

AB - The geometrical and vibrational characteristics of isolated H-bonded anionic complexes [FHFDF]−, [FHFTF]−, and [FDFTF]− are calculated quantum-mechanically. The four-dimensional anharmonic vibrational problems are solved by the variational method using the potential energy and dipole moment surfaces calculated in the MP2/6-311++G(3df,3pd) approximation with the basis set superposition error taken into account. Changes in the bond lengths of molecular fragments LF (L = H, D, T) and in the distances between the F− anion and the centers of mass of LF are used as the vibrational coordinates. For each isotopologue, the vibrational energy levels, the transition frequencies and absolute intensities for the H-bond and L–F stretching vibrations are determined. To study the isotope effects on the geometrical parameters, the values of internuclear separations and the asymmetry parameter of the F−L–F bridges, averaged over the ground state and several excited vibrational states, are calculated, as well as their standard

U2 - 10.1039/C1CP20696F

DO - 10.1039/C1CP20696F

M3 - Article

VL - 13

SP - 14019

EP - 14025

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 31

ER -