Spectroscopic interpretation: The high vibrations of CDBrClF

• Published in: The Journal of chemical physics Vol. 120; no. 9; pp. 4194 - 4206
• Main Authors: Jung, C., Mejia-Monasterio, C., Taylor, H. S.
• Format: Journal Article
• Language: English
• Published: United States 01.03.2004
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.1644795

We extract the dynamics implicit in an algebraic fitted model Hamiltonian for the deuterium chromophore’s vibrational motion in the molecule CDBrClF. The original model has four degrees of freedom, three positions and one representing interbond couplings. A conserved polyad allows in a semiclassical approach the reduction to three degrees of freedom. For most quantum states we can identify the underlying motion that when quantized gives the said state. Most of the classifications, identifications, and assignments are done by visual inspection of the already available wave function semiclassically transformed from the number representation to a representation on the reduced dimension toroidal configuration space corresponding to the classical action and angle variables. The concentration of the wave function density to lower dimensional subsets centered on idealized simple lower dimensional organizing structures and the behavior of the phase along such organizing centers already reveals the atomic motion. Extremely little computational work is needed.