Crossing of anisotropic and isotropic Raman components in the intermolecular resonance coupling of vibrations III-Ca(ClO4)2 and benzene solutions in acetone

✍ Scribed by Zbigniew Kęcki; Anna Sokolowska

• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 237 KB
• Volume: 26
• Category: Article
• ISSN: 0377-0486
• DOI: 10.1002/jrs.1250261108

✦ Synopsis

Abstract

Changes in the wavenumbers of the anisotropic and isotropic components of the C=O stretching band in the Raman spectrum of Ca(ClO~4~)~2~ and benzene solutions in acetone were investigated. Non‐coincidence values defined as Δ__v__ = v~aniso~ — v~iso~ for the C = O band in Ca(ClO~4~)~2~ solutions were positive (+ 5 cm^−1^) for bulk acetone and negative (—25 cm^−1^) for acetone‐shared ion pairs. In acetone solutions diluted with benzene there is a decrease in C = O non‐coincidence from +5 cm^−1^ down to about — 1 cm^−1^. The change of non‐coincidence sign appears at a benzene/acetone molar ratio of 10. The concept of third‐body mediation is applied to explain the observed changes of non‐coincidence in highly polar and non‐polar diluents.