Molecular properties magnetic field perturbations

Such second-order molecular properties as spin-spin coupling depend upon distortion of electron clouds by additional external perturbations that is, in the NMR experiment they depend upon the electronic motion induced by an applied magnetic field. Theories for such second-order molecular properties require a study of the change in the molecular-orbital wavefunctions, which may be found by using a perturbation method to describe the effects occurring when a magnetic field is applied.8-1065-67... 

Having considered the general expressions for first- and second-order molecular properties, we now restrict ourselves to properties associated with the application of static uniform external electric and magnetic fields. For such perturbations, the Hamiltonian operator may be written in the manner (in atomic units)... 

We shall limit attention to molecular properties arising from the introduction of external electric and magnetic fields through minimal coupling (118). In the next section we will consider specific fields for the moment we will focus on the general forms. The introduction of external fields leads to perturbation operators on the form... 

A large class of molecular properties arise from the interaction of molecules with electromagnetic fields. As emphasized previously, the external fields are treated as perturbations and so one considers only the effect of the fields on the molecule and not the effect of the molecule on the field. The electromagnetic fields introduced into the electronic wave equation is accordingly those of free space. From (79) one observes that in the absence of sources the electric field has zero divergence, and so both the electric and magnetic fields are purely transversal. It follows that the scalar potential is a constant and can be set to zero. In Coulomb gauge the vector potential is found from the equation... 

Recently, such universal tools for calculating electronic g matrices of molecular systems in a doublet state were developed, implemented, and validated [35,112,116]. These tools employ two-component eigenfunctions from relativistic DF calculations which take spin-orbit interaction into account self-consistent-ly [18,19] (see Section 2.3) in such a formalism, the parameter g is treated as a first-order property with the external magnetic field as the only perturbation, at... 

Liquid crystals are generally characterized by the strong correlation between molecules, which respond cooperatively to external perturbations. That strong molecular reorientation (or director reorientation) can be easily induced by a static electric or magnetic field is a well-known phenomenon. The same effect induced by optical fields was, however, only studied recently. " Unusually large nonlinear optical effects based on the optical-field-induced molecular reorientation have been observed in nematic liquid-crystal films under the illumination of one or more cw laser beams. In these cases, both the static and dynamical properties of this field-induced molecular motion are found to obey the Ericksen-Leslie continuum theory, which describe the collective molecular reorientation by the rotation of a director (average molecular orientation). 

In general, they can all be properly dealt with in the framework of perturbation (response) theory. According to the discussion in section 5.4, we may add external electromagnetic fields acting on individual electrons to the one-electron terms in the Hamiltonian of Eq. (8.66). Fields produced by other electrons, so that contributions to the one- and two-electron interaction operators in Eq. (8.66) arise, are not of this kind as they are considered to be internal and are properly accounted for in the Breit (section 8.1) or Breit-Pauli Hamiltonians (section 13.2). Although the extemal-field-free Breit-Pauli Hamiltonian comprises all internal interactions, such as spin-spin and spin-other-orbit terms, they may nevertheless also be considered as a perturbation in molecular property calculations. While our derivation of the Breit-Pauli Hamiltonian did not include additional external fields (such as the magnetic field applied in magnetic resonance spectroscopies), we now need to consider these fields as well. 

In its broadest sense, spectroscopy is concerned with interactions between light and matter. Since light consists of electromagnetic waves, this chapter begins with classical and quantum mechanical treatments of molecules subjected to static (time-independent) electric fields. Our discussion identifies the molecular properties that control interactions with electric fields the electric multipole moments and the electric polarizability. Time-dependent electromagnetic waves are then described classically using vector and scalar potentials for the associated electric and magnetic fields E and B, and the classical Hamiltonian is obtained for a molecule in the presence of these potentials. Quantum mechanical time-dependent perturbation theory is finally used to extract probabilities of transitions between molecular states. This powerful formalism not only covers the full array of multipole interactions that can cause spectroscopic transitions, but also reveals the hierarchies of multiphoton transitions that can occur. This chapter thus establishes a framework for multiphoton spectroscopies (e.g., Raman spectroscopy and coherent anti-Stokes Raman spectroscopy, which are discussed in Chapters 10 and 11) as well as for the one-photon spectroscopies that are described in most of this book. 

Table 2.1 Selected properties of molecular solutes defined as analytical derivatives of the basic PCM free-energy functional The perturbations are R, nuclear coordinates, E an external electric field, Em a Maxwell electric field in the medium (see Appendix), B an external magnetic field, /t/ a magnetic nuclear moment...

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