Rotational-angular-momentum relaxation mechanisms in the energy-corrected-sudden scaling theory
- 1 February 1995
- journal article
- research article
- Published by American Physical Society (APS) in Physical Review A
- Vol. 51 (2) , 1235-1240
- https://doi.org/10.1103/physreva.51.1235
Abstract
In calculating the infrared (IR) band shape for bending modes, the angular-momentum coupling between vibration, rotation, and radiation must be taken into account. The accuracy of the energy-corrected-sudden (ECS) model has been proved through many recent applications in isotropic Raman Q-branch profiles. Furthermore, this model is based on the physical infinite-order-sudden (IOS) approximation, which allows inclusion of the other relaxation mechanisms required when considering other spectroscopic branches, such as IR Q-bending bands. To include, in a consistent way, the role of the vibrational angular momentum in the rovibrational relaxation matrix, the relaxation of the rotational angular momentum J and of its associated higher-order tensors [J ,. . . (basically absent in the IOS approximation) is enforced in the present ECS model. Application to the 2076.86 infrared rovibrational band of leads to the determination of the [J relaxation time in agreement with previous values obtained from different measurements. The present theory may be applied to other spectroscopic bands, such as the anisotropic Raman ones.
Keywords
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