Cartesian Dynamics of Simple Molecules X Linear Quadratomics (C_∞v Symmetry)

Abstract

The vibrations of linear ABC₂ type molecules with C_∞V point group are analysed in terms of Cartesian co-ordinates. Algebraic expressions for the three stretching and two bending normal mode frequencies are derived in terms of longitudinal and transverse force constants, atomic masses and bond lengths. Values of non-valence interaction parameters are transferred from A₂B₂ (D_∞h) molecules, and values of the principal force constants are adjusted to reproduce the observed frequencies for a number of asymmetric halogen derivatives of acetylene. Normal mode frequencies of various isotopic species are also calculated. The nature of the computed eigenvectors for these molecules is briefly discussed. It is found that the carbon-carbon and carbon-hydrogen valence interactions remain approximately constant for these molecules, whereas the carbon-halogen bonds show a weakening trend with increasing halogen mass.

Key Words:

• Molecular vibrations
• infrared spectroscopy
• Raman spectroscopy
• lattice dynamics