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
Язык оригиналаанглийский
Страницы (с-по)14019-14025
Число страниц7
ЖурналPhysical Chemistry Chemical Physics
Том13
Номер выпуска31
DOI
СостояниеОпубликовано - 2011

ID: 5133354