Dirac equation molecular properties

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... 

In this section we briefly review the main properties of the Dirac equation that is the basic equation to start with to build a relativistic effective Hamiltonian for atomic and molecular calculations. This single particle equation, as already stated in the introduction, was established in 1928 by P.A.M Dirac [1] as the Lorentz invariant counterpart of the Schrodinger equation. On a note let us recall that the first attempts to replace the Schrodinger equation by an equation fulfilling the requirements of special relativity started just after quantum... 

In molecular property calculations the same mutual interplay of electron correlation, relativity and perturbation operators (e.g. external fields) occurs. For light until medium atoms relativistic contributions were often accounted for by perturbation theory facilitating quasirela-tivistic approximations to the Dirac-Hamiltonian [114-117]. It is well-known that operators like the Breit-Pauli Hamiltonian are plagued by essential singularities and therefore are not to be used in variational procedures. It can therefore be expected that for heavier elements per-turbational inclusion of relativity will eventually become inadequate and that one has to start from a scheme where relativitiy is included from the beginning. Nevertheless very efficient approximations to the Dirac equation in two-component form exist and will be discussed further below in combination with their relevance for EFG calculations. In order to calculate the different contributions to a first-order property as the EFG, Kello and Sadlej devised a multiple perturbation scheme [118] in which a first-order property is expanded as... 

Our discussion of spatial inversion symmetry concludes our project of demonstrating the symmetry properties of the Dirac equation under transformations of spin and spatial coordinates. With a spherical potential, the symmetry group is SU(2) 0 0(3). For potentials of lower (e.g., molecular) symmetries the appropriate group is SU (2)0G, where G is the nonrelativistic (spatial) point group of the potential—that is, the... 

However, the atomic solutions of the Dirac equation provide more than merely a guide to the choice of basis functions. The atoms in a molecule retain their atomic identities to a very large extent, and the modifications caused by the molecular field are quite small for most properties. In order to arrive at a satisfactory description of the relativistic effects in molecules, we must first of all be able to treat these effects at the atomic level. The insight gained into the effects of relativity on atomic structure is therefore a necessary and useful starting point for relativistic quantum chemistry. 

Most studies of molecular properties are founded on the response of the molecule to electromagnetic fields. A relativistic electronic system is described by the time-independent Dirac equation... 

We could continue now with the Dirac equation and derive expressions for the molecular properties using standard perturbation theory. However, as stated earlier, the exposition in these notes is restricted basically to a non-relativistic treatment with the exception that we want to include also interactions with the spin of the electrons. The appropriate operator can be found by reduction of the Dirac equation to a non-relativistic two-component form, which can be achieved by several approaches. Here, we want to discuss only the simplest approach, the so-called elimination of the small component. 

Energy levels of heavy and super-heavy (Z>100) elements are calculated by the relativistic coupled cluster method. The method starts from the four-component solutions of the Dirac-Fock or Dirac-Fock-Breit equations, and correlates them by the coupled-cluster approach. Simultaneous inclusion of relativistic terms in the Hamiltonian (to order o , where a is the fine-structure constant) and correlation effects (all products smd powers of single and double virtual excitations) is achieved. The Fock-space coupled-cluster method yields directly transition energies (ionization potentials, excitation energies, electron affinities). Results are in good agreement (usually better than 0.1 eV) with known experimental values. Properties of superheavy atoms which are not known experimentally can be predicted. Examples include the nature of the ground states of elements 104 md 111. Molecular applications are also presented. 

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