The distribution of intensities in a vibrational spectrum: a model computational study of the transition to classical chaos
β Scribed by J. Brickmann; Y.M. Engel; R.D. Levine
- Publisher
- Elsevier Science
- Year
- 1987
- Tongue
- English
- Weight
- 657 KB
- Volume
- 137
- Category
- Article
- ISSN
- 0009-2614
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β¦ Synopsis
A model Hamiltoman for two coupled oscillators is used to generate Franck-Condon factors corresponding to transitions between two displaced potential energy surfaces. The distribution of intensities is examined as a function of the energy of the initial state. The fluctuations in the intensities about their smooth envelope are found to diminish at higher initial energies when the correspondmg classuzal motion is more chaotic. The fluctuations remain, however, even in the fully chaotic limit. The distribution in that regime IS very closely fitted by one of maximum entropy subject only to a given oscillator strength.
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Relative intensities in the vibrational structure of the Γ1 A u (C 2h )-X 1 + g (D βh ) electronic transition of acetylene are calculated. The calculation takes account of the large change of geometry and the change in the normal coordinates (the DushinskiΓ effect) between the two states. Because co
The intersystem \(a^{3} \Pi-X^{1} \Sigma^{+}(0,0)\) transition of \(\mathrm{CS}\) has been recorded by means of Fourier transform spectrometry from a hot cathode, low-pressure emission source. Study of the relative line intensities in the three subbands shows interference effects appearing (i) betwe