The variation of molecular properties with vibration-rotation
Abstract
Molecular properties depend on the state of rotation and vibration. As a result of recent experimental developments such a dependence has been detected by several techniques for a variety of molecular properties of a large number of compounds. By expanding the property P as a power series in the reduced normal coordinates it is possible to derive an expression relating P to the state of rotation and vibration. In the present paper this is done for an asymmetric rotor molecule in a vibrational state (v1v2 … vN) and a rotational state (Jτ). Terms in the expansion of P up to those quartic in the reduced normal coordinates are taken into account. The expression is of the form
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where Pe(0) is the value of the property at equilibrium, PJτ, AiJτ and Bij depend on the parameters describing the potential energy surface and the property surface, and a superscript Jτ denotes a dependence on rotational state through the quantities <Jτ|Πα2|Jτ> where Πα denotes the rotational angular momentum about a principal axis of rotation.
- Publication:
-
Molecular Physics
- Pub Date:
- 1979
- DOI:
- 10.1080/00268977900102111
- Bibcode:
- 1979MolPh..38..877R