Studies on the Vibrational and Rovibrational Energies and Vibrational Force Constants of Diatomic Molecular States Using Algebraic and Variational Methods
✍ Scribed by Weiguo Sun; Shilin Hou; Hao Feng; Weiyi Ren
- Publisher
- Elsevier Science
- Year
- 2002
- Tongue
- English
- Weight
- 174 KB
- Volume
- 215
- Category
- Article
- ISSN
- 0022-2852
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✦ Synopsis
Alternative expressions for vibrational and rotational spectrum constants and energies of diatomic molecular electronic states based on perturbation theory are suggested. An algebraic method (AM) is proposed to generate a converged full vibrational spectrum from limited energy data, and a potential variational method (PVM) is suggested to produce the vibrational force constants f n and rotational spectrum constants using the perturbation formulae and the AM vibrational constants. The AM and PVM have been applied to study 10 diatomic electronic states: the X 1 + g and C 1 - u states of H 2 ; the X 1 + g , A 3 + u , B 3 - u , and B 3 g states of N 2 ; the X 3 - g , A 3 + u , and c 1 - u states of O 2 ; and the X 1 + g state of Br 2 . Calculations show that (1) the AM E υmax converges to the correct molecular dissociation energy; (2) the AM not only reproduce the input energies, but also generate the E υ 's of high vibrational excited states which may be difficult to obtain experimentally or theoretically; (3) the PVM vibrational force constants f n may be used to measure the relative chemical bondstrengths of different diatomic electronic states for a molecule quantitatively.