ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The extended virial theorem, obtained from a Fourier-Laplace transformation of equations of motion, is applied to the phenomenon of predissociation. The underlying resonance energy model rigorously defined by means of the theory of dilation analytic operators prescribes in detail the balance between the various energy contributions in a way analogous to the situation prevailing in a stationary system. The extended virial theorem is applied to predissociation, particularly in connection with the interpretation of the nearly degenerate G 1Π ∼ I 1Π energy spectrum in SiO. It was previously found for the rovibronic spectra assigned to G 1Π - X 1Σ+ and I1Π - X1 Σ+, that every G - X band is accompanied by a I - X band. Whereas the I 1Π state does not seem to undergo predissociation, the G state shows increasing predissociation with increasing vibrational quantum number. We show that the virial theorem generalized to include continuum phenomena offers an interpretation of the nearly degenerate spectra of SiO as well as of the concomitant isotope shift of SiO16 and SiO18 with respect to both resonance positions and widths.
Additional Material:
2 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560140410
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