Theoretical characterization of the lowest-energy absorption band of pyrrole

Roos, BjörnLund University,Lunds universitet,Beräkningskemi,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Computational Chemistry,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH (author)

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.

Malmqvist, Per-ÅkeLund University,Lunds universitet,Beräkningskemi,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Computational Chemistry,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)teok-pma (author)
Molina, VicentLund University,Lunds universitet,Beräkningskemi,Enheten för fysikalisk och teoretisk kemi,Kemiska institutionen,Institutioner vid LTH,Lunds Tekniska Högskola,Computational Chemistry,Physical and theoretical chemistry,Department of Chemistry,Departments at LTH,Faculty of Engineering, LTH(Swepub:lu)teok-vmo (author)
Serrano-Andres, L (author)
Merchan, M (author)
BeräkningskemiEnheten för fysikalisk och teoretisk kemi (creator_code:org_t)

In:Journal of Chemical Physics: AIP Publishing116:17, s. 7526-75360021-96061089-7690

By the author/editor: Roos, Björn; Malmqvist, Per-Å ...; Molina, Vicent; Serrano-Andres, ...; Merchan, M

About the subject

NATURAL SCIENCES: NATURAL SCIENCES; and Chemical Science ...; and Theoretical Chem ...

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