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RESEARCH PRODUCT
Multiconfigurational perturbation theory (CASPT2) applied to the study of the low-lying singlet and triplet excited states of cyclopropene
Manuela MerchánRemedios González-luqueBjörn O. Roossubject
PhysicsValence (chemistry)Spectral bandsCyclopropeneAtomic and Molecular Physics and OpticsSpectral linechemistry.chemical_compoundsymbols.namesakechemistryExcited stateIonizationRydberg formulasymbolsSinglet stateAtomic physicsdescription
The electronic spectrum of cyclopropene has been studied using multiconfigurational second-order perturbation theory (CASPT2) with extended ANO-type basis sets. The calculation comprises two valence states and the 3s, 3p, 3d members of the Rydberg series converging to the π and σ ionization limits. A total of twenty singlet and twenty triplet excited states have been analyzed. The results confirm the valence nature of the lowest energy singlet-singlet band and yield a conclusive assignment: the first dipole-allowed transition in cyclcopropene is due to absorption to a (σ → π*) state. The (π → π*) (V) state is interleaved among a number of Rydberg states in the most intense band of the system. The remaining spectral bands are due to Rydberg transitions of higher energy. The two lowest singlet-triplet transitions involve the same valence states. The results are in agreement with available experimental data and provide a number of new assignments of the experimental spectra.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 1996-09-01 | Zeitschrift f�r Physik D Atoms, Molecules and Clusters |