Configuration interaction calculations on the X1Sigma+ground state and low-lying A1Pi and1Delta excited states of the PN molecule. II. Potential energy curves of the A1Pi and1Delta excited states of PN and spectroscopic properties
| Autor: | J J A Koot, David Feller, G de Brouckere |
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| Rok vydání: | 1993 |
| Předmět: | |
| Zdroj: | Journal of Physics B: Atomic, Molecular and Optical Physics. 26:1915-1934 |
| ISSN: | 1361-6455 0953-4075 |
| DOI: | 10.1088/0953-4075/26/13/014 |
| Popis: | For pt.I see ibid., vol.25, no.21, p.4433-46 (1992). CI calculations have been performed on the A 1 Pi and 1 Delta states of PN in the vicinity of their respective equilibrium geometries, yielding spectroscopic constants in good agreement with the available experimental data. The 1 Delta state, which is unknown experimentally, is predicted to lie less than 500 cm-1 above the 1 Pi state and 40345 cm-1 above the 1 Sigma + ground state. Theoretical vibrational bands for the A 1 Pi to X 1 Sigma + transition were computed, along with the corresponding Franck-Condon factors. The calculated vibrational transitions agree quite well with the observed values while the Franck-Condon factors compare favourably with those calculated semiempirically from observed vibrational transition probabilities. Spontaneous radiative and non-radiative lifetimes derived according to two decay mechanisms-a cascade (A 1 Pi state being 'isolated') mechanism and an electric dipolar transition mechanism-show that the latter mode of decay is several orders of magnitude larger. The single experimentally known lifetime value, i.e. for nu '=0, issued from this decay mode agrees reasonably well with the calculated value. |
| Databáze: | OpenAIRE |
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