ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
The self-consistent field (SCF) method beyond its computational advantage lends meaning to the concept of local modes and its applicability implies mode specificity in the unimolecular reaction being studied. The natural expansion (NE) analysis of stable or metastable vibrational states is presented here first. The NE analysis enables us to determine the applicability of the SCF approximation, the optimal molecular modes for any given vibrational energy and therefore provides a positive test for mode specificity. Moreover, it is shown here that even when the internal coordinates of the Hamiltonian are not optimized and there are several dominant configurations in the NE, mode specificity can be indicated by analyzing these configurations. As examples, the mode specificity in the unimolecular decomposition of CO2 to CO+O and in the dissociation of formaldehyde to H2+CO are studied by the NE analysis.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.449104
Permalink
