Multiconfigurational perturbation theory (CASPT2) applied to the study of the low-lying singlet and triplet excited states of cyclopropene |
| |
Authors: | R González-Luque M Merchán B O Roos |
| |
Institution: | 1. Departamento de Química Física, Universitat de València, Dr. Moliner 50, Burjassot, E-46100, Valencia, Spain 2. Department of Theoretical Chemistry, Chemical Center, P.O. Box 124, S-221 00, Lund, Sweden
|
| |
Abstract: | 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. |
| |
Keywords: | |
本文献已被 SpringerLink 等数据库收录! |
|