Assignment and simplified Hamiltonian for molecular vibrations obtained by an improved diabatic correlation method

作者：Diaz A; Jung C^*

来源：Molecular Physics, 2010, 108(1): 43-49.

DOI：10.1080/00268970903496645

• molecular vibrations
• diabatic correlation
• assignment

The assignment of molecular vibrations by diabatic correlation diagrams does not work in the form originally implemented by Rose and Kellman [J. Chem. Phys. 105, 7348 (1996)] for the class of states of CHBrClF where the two bend modes couple to rotating and counter-rotating motion. We show that an improved version of diabatic correlation, where we allow the variation of some additional parameters, works quite well. This improved diabatic correlation also provides a simplified Hamiltonian for the class of states under study. The results coming out of the improved correlation method are compared with the assignment coming out of a graphical method [C. Jung, E. Ziemniak, and H.S. Taylor, J. Chem. Phys. 115, 2499 (2001)]; they coincide perfectly.

• 出版日期2010