Cotton—Mouton effect

Molecular electric quadrupole moments are more elusive animals, and they are not particularly easy to determine experimentally. Prior to 1970, the only direct routes to these quantities were from the Kerr and Cotton-Mouton effects. They can now be obtained from microwave Zeeman spectroscopy, to fair accuracy. It is fair to say that direct calculation offers a faster and more reliable route to this property than experiment. 

Note 3 The divergence temperature for nematogens can be measured by using the Kerr effect or Cotton-Mouton effect or by light-scattering experiments. 

Cotton-Mouton effect), NMR chemical shift and coupling constants, the optical rotation of polarized light and correlation coefficients between different properties. Extensions to incorporate long-range interactions have also been elaborated11 and it has even been possible to adapt RIS theory for the description of the dynamics of transitions between rotational isomeric states.12,13... 

The second high-frequency term involves a sum over all discrete states and an integration over the continuum states the difficulties involved have been outlined before. Little is known about the continuum states, but what few calculations there are for simple systems92 suggest that they may be at least as important as the discrete states. For this reason early calculations were done in the closure approximation, notably by Van Vleck in the 1930 s. The difficulties of calculating xHF have been reviewed by Weltner.93 Experimentally xHF may be obtained from rotational magnetic moments. For linear molecules these can be obtained from molecular-beam experiments, which also measure the anisotropy x Xi- directly. The anisotropies may also be derived from crystal data, the Cotton-Mouton effect and, recently, Zeeman microwave studies principally by Flygare et al.9i... 

Bishop has recently been studying the magnetic properties of small systems (including the Cotton-Mouton effect and the Faraday effect), once again providing accurate values with which the experiments can be judged. As well, his concerns with the effects of magnetic fields on vibrations have received widespread attention. 

Rizzo reviews in a unitary framework computational methods for the study of linear birefringence in condensed phase. In particular, he focuses on the PCM formulation of the Kerr birefringence, due to an external electric field yields, on the Cotton-Mouton effect, due to a magnetic field, and on the Buckingham effect due to an electric-field-gradient. A parallel analysis is presented for natural optical activity by Pecul Ruud. They present a brief summary of the theory of optical activity and a review of theoretical studies of solvent effects on these properties, which to a large extent has been done using various polarizable dielectric continuum models. 

The correlation factor jRcn(y) is specific to and determinable from the Cotton-Mouton effect " as well as from anisotropic light-scattering A. Piekara, Con t. rend., 1939, 208, 990. 

Rizzo and Coriani233 have used coupled cluster ab initio methods to calculate the Jones birefringence of He, Ne, Ar and Kr (and also for H2, N2, C2H2 and CO) and compare the values with the birefringence induced by the Cotton-Mouton effect. They find that the latter is between 100 and 3500 times larger than the former. 

The birefringence in external electric and magnetic fields (the Kerr and Cotton-Mouton effects) can be explained by the anisotropy of the properties of the medium that is due to either the orientation of anisotropic molecules in the external field (the Langevin-Bom mechanism) or the deformation of the electric or magnetic susceptibilities by this field, i.e., to hyperpolarizabilities (Voight mechanism). The former mechanism is effective for molecules that are anisotropic in the absence of the field and... 

Cotton-Mouton Effect in Gases of Molecules in Electronic States G3i2... 

The classical ideas about the isotropy of electrical properties of spherical-top molecules are usually extrapolated to the magnetic properties. This leads to the conclusion about the isotropy of the magnetic susceptibility in high-symmetry molecules and hence about the disappearance of the orientational contribution to the birefringence in magnetic fields (the Cotton-Mouton effect). In the case of degenerate electronic terms or in the pseudodegeneracy situation, these conclusions are incorrect and have to be reconsidered. 

Cotton-Mouton effect. (magnetic double refraction). Double refraction produced in some pure liquids by a magnetic field transverse to the hght beam. 

The present contribution reviews recent advances in the highly accurate calculation of frequency-dependent properties of atoms and small molecules, electronic struc-mre methods, basis set convergence and extrapolation techniques. Reported applications include first and second hyperpolarizabilities, Faraday, Buckingham and Cotton-Mouton effects as well as Jones and magneto-electric birefringence... 

In the next section we summarize the theoretical background for coupled cluster response theory and discuss certain issues related to their actual implementation. In Sections 3 and 4 we describe the application of quadratic and cubic response in calculations of first and second hyperpolarizabilities. The use of response theory to calculate magneto-optical properties as e.g. the Faraday effect, magnetic circular dichroism, Buckingham effect, Cotton-Mouton effect or Jones birefringence is discussed in Section 5. Finally we give some conclusions and an outlook in Section 6. 

---