Intramolecular and intermolecular interactions in methyl substituted pentanes as revealed by high energy CH-stretching overtone spectra

Publisher Website
Google Scholar
Abstract
The overtone spectra of pentane and 12 methyl substituted pentanes are measured in the liquid phase in the region of the pure local mode overtones corresponding to ΔvCH = 3, 4, 5, and 6. The local mode structure of the spectra is discussed. The local mode frequencies ωCH and diagonal local mode anharmonicities XCH for the methyl oscillators are obtained from an analysis of the spectra. The change in ωCH and XCH with increased methyl substitution is related to a barrier to large amplitude vibrational motion arising from steric crowding. The height of this barrier is obtained from dissociation energies calculated from ωCH and XCH by taking the local methyl CH stretching potential to be a Lippincott–Schroeder potential. The methyl steric interactions are described in terms of nonbonded Lennard-Jones and Morse potentials. The parameters for these nonbonded potentials are calculated from the barrier heights and structural information obtained from molecular models for their least strained conformations. These parameters are used to identify a positional dependence in methyl steric hindrance. Force constants evaluated from the nonbonded potentials are correlated with bulk liquid properties.

This publication has 24 references indexed in Scilit: