Per-Åke Malmqvist
Senior lecturer
Ab initio characterization of C-5
Author
Summary, in English
In this paper, the structure and spectroscopic parameters of the C-5 cluster are determined using multiconfigurational quantum chemical methods as implemented in the MOLCAS software. A number of spectroscopic properties (band center positions, l-doubling parameters, and rotational constants) have been characterized. From the new results, the assignments of previous astrophysical observations [J. Goicoechea , Astrophys. J. 609, 225 (2004)] are discussed. A detailed exploration of the global potential energy surface confirms that C-5 has a X (1)Sigma(+)(g) linear isomer of prominent stability and, at least, three minimum energy structures showing singlet electronic ground states. Two of them are cyclic and one has a nonplanar geometry. Vertical and adiabatic electronic transitions and vibrational spectroscopic parameters are determined for the most stable linear isomer using multiconfigurational second order perturbation theory (CASPT2) using an active space containing 12 valence orbitals with 12 active electrons and extended ANO-type basis sets. The infrared spectrum has been analyzed from an anharmonic force field derived form the local surface, determined from the energies of a grid of 1350 geometries. The force field includes four coupling terms. The CASPT2 band center position of the nu(7)(pi(u)) anharmonic fundamental has been calculated to be at 102 cm(-1), which validates the assignment to C-5 of the pattern of bands centered at 102 cm(-1) observed with the ISO telescope. (C) 2007 American Institute of Physics.
Department/s
- Computational Chemistry
Publishing year
2007
Language
English
Publication/Series
Journal of Chemical Physics
Volume
127
Issue
15
Links
Document type
Journal article
Publisher
American Institute of Physics (AIP)
Topic
- Theoretical Chemistry (including Computational Chemistry)
Status
Published
ISBN/ISSN/Other
- ISSN: 0021-9606