By Boschke F.L.
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Extra resources for Bonding Structure
Acknowledgements. We are glad to t h a n k a number of colleagues for advice and critical reading o~ the manuscript, particularly Drs E. V. Lassak, P. J. Stiles, A. M. Sargeson and T. Thirunamachandran. 46 Discriminating Interactions Between Chiral Molecules VI. References Albert, A. , 1973, Chapman. : J. Biol. Chem. 100, 249 (1933). Barnes, D. , Pettit, L. : Chem. Commun. 1970, 1000. Barnes, G. , Backhouse, J. , Dwyer, F. , Gyarfas, E. : Proc. Roy. Soc. W. 89, 151 (1956). Bennet, W. : J. Am. Chem.
4. Orientation Averages of the Discrimination The question how to apply these results to actual chemical situations is not straightforward. 11) but the meaning of discrimination energy is then the difference between d-d and d-l energies each calculated for the optimum d and l orientations. Since these orientations are determined to some degree b y all the forces acting, and certainly not only by the dispersion forces, they cannot be treated ill a systematic way. In other situations than a crystal lattice it is perhaps realistic to suppose that at distances greater than those for contacts between closed shells the molecules have one axis in each fixed relatively to the other, but are free to rotate about that axis.
There is thus an overall sign change of dEE-•, which discriminates between d-d and d-l interactions. A simplification of (III. 11) is to restrict it to a single pair of upper levels n a and n b, by assuming that the transition moments to this pair dominate. The simpler expression is given in (III. 12) where (R,k)0. 13) The quantities defined in expression (III. 13) are the components of the opticalrotatory pseudotensor. R0~ a transforms under rotations like the second rank tensor for the quadrupole moment ex, xj, but is antisymmetric to inversion in the origin.