Transition dipole moment magnetic

Vibrational circular dichroism arises from the interference of the electric dipole transition moment (p joi and the magnetic dipole transition moment (m )io and is proportional to the rotational strength, / ,o, where... 

Denoting the electric and magnetic dipole transition moments of oscillators a and b as p, lUg and m, lUb, respectively, the rotational strength of the coupled oscillator is given by (34)... 

The spectra in this figure represent one of the strongest cases for the ring current mechanism of VCD intensity enhancement. In this case, currents increase the magnetic dipole transition moment without altering the relative arrangement of electric dipole transition moments and the relative intensity pattern is preserved. In the structures 42 and 43, we show that in the A complex, 42,... 

The formulation of magnetic dipole transition moments is unfortunately less straightforward. Compare the electronic contributions to the electric and magnetic dipole moments of G ... 

Thus, we feel that the a-helical and the extended" helical structure are well established in VCD, and that there exists a simple method for the interpretation of the data. The VCD features of the B-pleated sheet structure appear reasonably well established, too, although its interpretation is much more difficult. Since the data are mono-signate, the DECO model is not appropriate (it always predicts conservative couplets). Nafie and coworkers explained such monosignate VCD in terms of a model similar to one described earlier by Schellman [24], with nearly co-linear (and antiparallel) electric and magnetic dipole transition moments [30]. 

The ellipticity, or the intensity of the circular dichroism (CD) spectrum, is fundamentally characterized by the rotatory strength R, which is given by the imaginary part of the inner product between the electronic and magnetic dipole transition moment vectors ... 

Here i//0 is the ground vibrational wave function and ij/ is the wavefunction corresponding to the first excited vibrational state of the th normal mode /< is the electric dipole moment operator Qj is the normal coordinate for the /th vibrational mode the subscript 0 at derivative indicates that the term is evaluated at the equilibrium geometry. The related rotational strength or VCD intensity is determined by the dot product between the electric dipole and magnetic dipole transition moment vectors, as given in (2) ... 

Stephens PJ (1987) Gauge dependence of vibrational magnetic dipole transition moments and rotational strengths. J Phys Chem 91 1712-1715... 

The magnetic dipole transition moment on the other hand formulates as ... 

Situated in the same environment the optical activity of N3 will be smaller than that of the carbonyl group, mainly because its magnetic dipole transition moment is smaller by a factor of 5. This is because in the azido group the n and tt orbitals are more separated in space than in]>CO. Thus in all optically active alkyl azides which have been tested, the rotatory contribution of the 285 nm band is entirely negligible, while many analogous aldehydes do show Cotton effects... 

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