Abstract
We have calculated the vibrational solvent shifts of the fundamental bands of HCl diluted in Ar, Kr, and Xe solutions at different thermodynamic conditions by means of the molecular dynamics technique and a model for the isotropic part of the interaction depending on the vibration. The theoretical vibrational shifts, which were compared with the available experimental data, have been determined by considering both, the usual linear Buckingham terms and the nonlinear anharmonic corrections, and the latter omitted in a previous work for the HCl in Ar and Kr. We have found that the Buckingham contributions dominate the solvent shifts of the fundamental bands of HCl in Ar, Kr, and Xe, although the anharmonic shifts’ present significant greater values than those obtained previously for N2 diluted in liquid Ar and pure liquid N2, both at normal conditions. We have analyzed the solvent shifts influence of the linear and quadratic (in the vibrational coordinate) oscillator-bath interaction terms and also the Dunham intramolecular potential effects on the anharmonic contributions.
Highlights
The study of the fundamental and overtones infrared and Raman vibrational solvent shifts gives relevant information about the molecular interaction depending of the intramolecular vibration [1,2,3,4,5,6,7]
We have calculated the vibrational solvent shifts of the fundamental absorption bands of the HCl diluted in Ar, Kr, and Xe by means of the molecular dynamics simulation and the model proposed by Marteau et al [9] for the isotropic part of the interaction depending of the vibration
[8], we have taken into account the non-linear anharmonic contribution to the solvent shift, obtaining a reasonable agreement between the theoretical and the experimental solvent shifts
Summary
The study of the fundamental and overtones infrared and Raman vibrational solvent shifts gives relevant information about the molecular interaction depending of the intramolecular vibration [1,2,3,4,5,6,7]. In an earlier work, according to Buckingham, it was deduced that the diatomic solvent shift associated to the vibrational transition 0 → ν of a cubic anharmonic oscillator presents a linear dependence with the vibrational quantum number ν [1]. This result, which is valid in principle for the fundamental band or lower overtones of several diatomics, would break down for the fundamental bands of some molecules and high overtones of much ones.
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