1,4-Dimethylenespiropentane: a unique model system for studying fermi resonance in raman optical activity
- Hug, Werner Department of Chemistry, University of Fribourg, Switzerland
- Haesler, Jacques Department of Chemistry, University of Fribourg, Switzerland
- Kozhushkov, Sergei I. Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Germany
- Meijere, Armin de Institut für Organische und Biomolekulare Chemie der Georg-August-Universität Göttingen, Germany
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11.05.2007
Published in:
- ChemPhysChem. - 2007, vol. 8, no. 8, p. 1161 - 1169
English
The C₂-symmetric title compound, a small, rigid hydrocarbon molecule with two distinct, strongly interacting vibrational chromophores, represents a unique model system for testing computational approaches to Raman optical activity (ROA) beyond the isolated molecule and the harmonic approximation. We show that the experimental Raman and ROA spectra are marked by the presence of strong Fermi resonances, and that the shape and relative size of the bands which we attribute to such resonances strongly depend on the solvent environment of the molecule. On the other hand, the dominant computed ROA couplet, arising from the C==C stretching vibrations, is absent in the spectra measured in the condensed phase. The strong dependence of the computed size of the couplet on the description of the diffuse part of the electron distribution suggests that this absence is due to nonspecific interactions in the condensed phase.
- Faculty
- Faculté des sciences et de médecine
- Department
- Département de Chimie
- Language
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- English
- Classification
- Chemistry
- License
- License undefined
- Identifiers
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- RERO DOC 8124
- DOI 10.1002/cphc.200600678
- Persistent URL
- https://folia.unifr.ch/unifr/documents/300464
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