Thermodynamic functions for vibronic systems

✍ Scribed by S. S. Crotov; A. A. Ischenko; L. S. Ivashkevich

• Publisher: John Wiley and Sons
• Year: 1979
• Tongue: English
• Weight: 422 KB
• Volume: 16
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560160504

✦ Synopsis

Abstract

A method is introduced which simplifies the derivation of equations for the calculation of statistical sums for vibronic systems. Within the “independent ordering approximation” analytical expressions are found for thermodynamic functions for molecules with degenerate electronic ground state (E−β and E − e types of degeneracies). Vibronic interactions are shown to yield an additional thermodynamic stabilization. The computations were carried out for VCl~4~ and VBr~4~ with doubly degenerate electronic ground states. For these molecules the effect is shown to be small.