Spin-orbit interaction, second-order

On matrix form the non-unitary transformations (27) and (30) of the previous section are easily extended to the complete Hamiltonian and have therefore allowed relativistic and non-relativistic spin-free calculations of spectroscopic constants and first-order properties at the four-component level (see, for instance. Refs. [45 7]). In this section, we consider the elimination of spin-orbit interaction in four-component calculations of second-order electric and magnetic properties. Formulas are restricted to the Hartree-Fock [48] or Kohn-Sham [49] level of theory, but are straightforwardly generalized. 

We then turn to the question of how to eliminate the spin-orbit interaction in four-component relativistic calculations. This allows the assessment of spin-orbit effects on molecular properties within the framework of a single theory. In a previous publication [13], we have shown how the spin-orbit interaction can be eliminated in four-component relativistic calculations of spectroscopic properties by deleting the quaternion imaginary parts of matrix representations of the quaternion modified Dirac equation. We show in this chapter how the application of the same procedure to second-order electric properties takes out spin-forbidden transitions in the spectrum of the mercury atom. Second-order magnetic properties require more care since the straightforward application of the above procedure will extinguish all spin interactions. After careful analysis on how to proceed we... 

Consider a dn configuration present in a crystal field that leaves the ground state nondegenerate except for spin. The ground state then consists of (25+ l)-spin states and the effect of the spin-orbit interaction plus the magnetic field can be computed using first- and second-order perturbation theory. If we take as the perturbation operator... 

There are three terms which appears in the first order relativistic expression the mass-velocity tehn, the Darwin term and the spin-orbit term[12]. Out of these terms the first two are comparatively easy to calculate, while the spin-orbit interaction term is more complicated. Fortunately, the spin-orbit interaction is often not too important for chemical properties, at least for the second row transition elements. It is therefore usual to neglect it in quantum chemical calculations. 

Spin-orbit interactions mix states with the same J but different L 8 by second (or higher) order perturbations, such perturbations become important when the separation between the levels is small. The spin-orbit coupling constants ( 4/) increase more rapidly through the rare earth series with increasing number of /-electrons than do the F s. This results in the breakdown of L 8 coupling even more near the middle of the rare earth series, because of the greater population of the upper... 

Besides fine-structure splitting, the occurrence of spin-forbidden transitions is the most striking feature in which spin-orbit interaction manifests itself. Radiative spin-forbidden transitions in light molecules usually take place at the millisecond time scale, if the transition is dipole allowed. A dipole- and spin-forbidden transition is even weaker, with lifetimes of the order of seconds. Proceeding down the periodic table, spin-forbidden transitions become more and more allowed due to the increase of spin-orbit coupling. For molecules containing elements with principal quantum number 5 or higher (and the late first-row transition metals Ni and Cu), there is hardly any difference between transition probabilities of spin-allowed and spin-forbidden processes. 

Two ions are well-known for their highly anisotropic properties. Firstly, in the rare-earth family, Dy3+ which has a 6H15/2 ground state. The spin-orbit interaction is stronger than the crystal field effects. The ratio J /J can be of the order of 100 (Jj. = 0), gjj = 20 and gi = 0 this is practically an ideal case. Secondly, in the transition element series, the ion Co2+ is also characterized by anisotropic interactions (either in the tetrahedral or octahedral coordination), the anisotropy being however lower than in the case of Dy3+. J /J is about 0.5 for this ion. Some Fe2+ compounds also display a behavior approximating to the Ising model. 

We now turn our attention to the second-order contributions. In order to see how these are derived, let us consider in particular the contributions of the spin-orbit interaction, 3u o. Before we can use second-order perturbation theory to evaluate these contributions, we need to write down the general matrix elements of this operator. We can do this easily if we write the expression in equation (7.72) in the simplified form... 

The rank k can take values 0, 1 and 2 by the triangle rule. Of these, the scalar term with k = 0 has no A dependence and hence does not affect the relative positions of the ro-vibrational energy levels. It just makes a small contribution to the electronic energy of the state r], A). The first-rank term produces a second-order contribution to the spin orbit interaction because it is directly proportional to the quantum number A from the 3-j symbol in the first line of (7.119). The contribution to the spin-orbit parameter A(R) which arises in this way is given (in cm-1) by... 

O. Vahtras, H. Agren, P. Jorgensen, H. J. J. A. Jensen, and T. Helgaker, The Second-Order Energy Contribution from the Spin-Orbit Interaction Operator to the Potential Energy Curve of Cr2, Int. J. Quantum Chem. 41,729-731 1992. 

In the above equation, A is the average second-order contribution due to the spin-orbit interaction. If we identify < Sz > with M, we can determine... 

Most transition metal ions have the orbital motion quenched to first order by the crystal field, but the presence of a large spin-orbit interaction coupled with Eq. (32) will cause second-order orbital terms in the hyperfine interaction of the magnitude... 

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