Molecular optical rotation: an evaluation of semiempirical models

Polavarapu, Prasad L.; Chakraborty, Dilip K.; Ruud, Kenneth

doi:10.1016/s0009-2614(00)00157-3

Cited by 57 publications

(43 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…45 There has been only one report to date on specific rotations 46 using CC theory, and one report on specific rotations 31 using CASSCF theory, so these two methods will not be elaborated upon in this article. The HF theory does not include the effects of electron correlation, while DFT incorporates these effects using density functionals.…”

Section: Quantum Mechanical Methodsmentioning

confidence: 99%

“…This model has subsequently been used to develop 30 a general set of parameters M i from the observed rotations in a series of molecules and then these parameters were used for the prediction of optical rotations of related molecules. For convenience in discussion, this model was referred 31 to as the dihedral sin sum (DSS) model. Whiffen's hypothesis of sin dependence is in contradiction to Kirkwood's polarizability model, which predicts a sin 2 dependence (vide infra).…”

Section: Whiffen's Empirical Modelmentioning

confidence: 99%

“…Whiffen's hypothesis of sin dependence is in contradiction to Kirkwood's polarizability model, which predicts a sin 2 dependence (vide infra). Furthermore, DSS model was shown recently 31 to fail in allene types of molecules. 8 Brewster's empirical rules are based on the hypothesis that "a center of optical activity can usefully be described as an asymmetric screw pattern of polarizability."…”

Section: Whiffen's Empirical Modelmentioning

confidence: 99%

“…33 Also, Kirkwood model predictions were found recently to match the quantum mechanical predictions in some molecules. 31 Barron 34 showed that if the two interacting groups i and k each have C nv (n > 2) symmetry, then the contribution from those two groups to the specific rotation in Eq. [6] will have a sin 2 dependence, where is the dihedral angle between groups i and k.…”

Section: Brewster's Empirical Rulesmentioning

confidence: 99%

See 3 more Smart Citations

Optical rotation: Recent advances in determining the absolute configuration

2002

Self Cite

View full text Add to dashboard Cite

The field of optical rotations is currently undergoing a renaissance, which is a direct result of the advances in quantum mechanics and the availability of faster desktop computers. In the last few years, the field of optical rotations has taken an important role for determining the three-dimensional molecular structure (absolute configuration and conformations) with confidence. The purpose of this review is to present the latest advances in this area so that practicing chemists can utilize them in their respective areas of research and development.

show abstract

Section: Quantum Mechanical Methodsmentioning

confidence: 99%

Section: Whiffen's Empirical Modelmentioning

confidence: 99%

Section: Whiffen's Empirical Modelmentioning

confidence: 99%

Section: Brewster's Empirical Rulesmentioning

confidence: 99%

See 2 more Smart Citations

Optical rotation: Recent advances in determining the absolute configuration

2002

Self Cite

View full text Add to dashboard Cite

show abstract

“…Only recently quantum chemical ab initio techniques provide sprectra of sufficient accuracy for that purpose [1,2,3,4]. On the other hand, due to their unique optical properties, chiral materials are of interest on their own: Chiral materials belong to the larger class of bi-isotropic or, even more generally, bianisotropic materials [5,6,7].…”

Section: Introductionmentioning

confidence: 99%

Optical activity in the Drude helix model

Dufey

2006

Chemical Physics

View full text Add to dashboard Cite

An old classical one-particle helix model for optical activity, first proposed by Drude, is reconsidered here. The quantum Drude model is very instructive because the optical activity can be calculated analytically without further approximations apart from the Rosenfeld long wavelength approximation. While it was generally believed that this model, when treated correctly, is optically inactive, we show that it leads to optical activity when the motion of the particle is quantum mechanically treated. We also find that optical activity arises even in the classical regime at non-zero energy, while for zero energy the model is inactive, in accordance with previous results. The model is compared with other one-electron models and it is shown that its predicted optical activity is qualitatively different from those of other one-electron systems. The vanishing of optical activity in the classical zero-energy limit for the Drude model is due to the localization of the particle at the equilibrium position, whereas in the analogous model of a particle moving freely on a helix without a definite equilibrium position, optical activity does not vanish but the spectrum is rescaled. The model under study leads to interesting predictions about the optical properties of e. g. helicene derivatives.

show abstract

High‐Accuracy Quantum Chemistry and Chiroptical Properties

Crawford

2011

Comprehensive Chiroptical Spectroscopy

View full text Add to dashboard Cite

Molecular optical rotation: an evaluation of semiempirical models

Cited by 57 publications

References 23 publications

Optical rotation: Recent advances in determining the absolute configuration

Optical rotation: Recent advances in determining the absolute configuration

Optical activity in the Drude helix model

High‐Accuracy Quantum Chemistry and Chiroptical Properties

Contact Info

Product

Resources

About