Electronic relaxation and molecular vibrations; transition-metal complexes and the valence shell force field

Abstract

The pseudo-Jahn–Teller formalism is used to devise a partitioning of vibrational force constant, particularly applicable to the study of transition-metal complexes. Parameters derived from this Valence Shell Force Field (VSFF) are readily correlated with the molecular orbital scheme of the complex. The scheme is used to investigate the relationship between π-bonding, the bond–bond interaction constant of the General Quadratic Force Field, and i.r. intensities in metal hexacarbonyls and hexacyanides.