Theoretical characterization of the lowest-energy absorption band of pyrrole

Björn Roos, Per-Åke Malmqvist, Vicent Molina, L Serrano-Andres, M Merchan

Research output: Contribution to journalArticlepeer-review

110 Citations (SciVal)

Abstract

The lowest-energy band of the electronic spectrum of pyrrole has been studied with vibrational resolution by using multiconfigurational second-order perturbation theory (CASPT2) and its multistate extension (MS-CASPT2) in conjunction with large atomic natural orbital-type basis sets including Rydberg functions. The obtained results provide a consistent picture of the recorded spectrum in the energy region 5.5-6.5 eV and confirm that the bulk of the intensity of the band arises from a pipi(*) intravalence transition, in contradiction to recent theoretical claims. Computed band origins for the 3s,3p Rydberg electronic transitions are in agreement with the available experimental data, although new assignments are suggested. As illustrated in the paper, the proper treatment of the valence-Rydberg mixing is particularly challenging for ab initio methodologies and can be seen as the main source of deviation among the recent theoretical results as regards the position of the low-lying valence excited states of pyrrole. (C) 2002 American Institute of Physics.
Original languageEnglish
Pages (from-to)7526-7536
JournalJournal of Chemical Physics
Volume116
Issue number17
DOIs
Publication statusPublished - 2002

Bibliographical note

The information about affiliations in this record was updated in December 2015.
The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)

Subject classification (UKÄ)

  • Theoretical Chemistry

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