Abstract
We present a detailed investigation of the perturbation approach for calculating zero-point vibrational contributions to molecular properties. It is demonstrated that if the sum of the potential energy and the zero-point vibrational energy is regarded as an effective potential energy, the leading contribution to the first-order wave function vanishes in the perturbation approach. Two different perturbation approaches have been investigated numerically by calculations of some magnetic properties for a few diatomic molecules and the results obtained have been compared to the exact numerical results. It is shown that only a few terms need to be included in a perturbation expansion to obtain an accuracy in the calculated rovibrational contribution better than the quality normally obtained for the potential and property surfaces in electronic structure calculations.
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Schedule a callMore From: Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta)
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