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Wiberg KB, Wang YG, Wilson SM, et al. Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone. J Phys Chem A. 2006;110(51):13995-4002doi: 10.1021/jp0655221.
Wiberg, K. B., Wang, Y. G., Wilson, S. M., Vaccaro, P. H., & Cheeseman, J. R. (2006). Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone. The journal of physical chemistry. A, 110(51), 13995-4002. https://doi.org/10.1021/jp0655221
Wiberg, Kenneth B, et al. "Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone." The journal of physical chemistry. A vol. 110,51 (2006): 13995-4002. doi: https://doi.org/10.1021/jp0655221
Wiberg KB, Wang YG, Wilson SM, Vaccaro PH, Cheeseman JR. Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone. J Phys Chem A. 2006 Dec 28;110(51):13995-4002. doi: 10.1021/jp0655221. PMID: 17181361.
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J Phys Chem A. 2006 Dec 28;110(51):13995-4002. doi: 10.1021/jp0655221.

Sum-over-states calculation of the specific rotations of some substituted oxiranes, chloropropionitrile, ethane, and norbornenone.

The journal of physical chemistry. A

Kenneth B Wiberg, Yi-Gui Wang, Shaun M Wilson, Patrick H Vaccaro, James R Cheeseman

Affiliations

  1. Department of Chemistry, Yale University, New Haven, CT 06520-8197, USA. [email protected]

PMID: 17181361 DOI: 10.1021/jp0655221

Abstract

A sum-over-states approach has been applied to the calculation of the specific rotations of several substituted oxiranes, 2-chloropropionitrile, and 30 degrees-rotated ethane. In each case, the first few excited states proved to have only a relatively small effect on the calculated specific rotation. It was necessary to use a very large number of excited states in order to achieve convergence with the results of the more direct linear response method. However, the latter does not give information on which excited states are important in determining the specific rotation. Norbornenone is unique in that its greatly enhanced specific rotation as compared to norbornanone is associated with the low-energy n-pi* transition. The C=C bond orbitals interact with the C=O in the LUMO, and a density difference plot for going from the ground state to the first excited state clearly shows the perturbation of the C=C.

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