Dirac-Coulomb equation

Abstract. An application of the Rayleigh-Ritz variational method to solving the Dirac-Coulomb equation, although resulted in many successful implementations, is far from being trivial and there are still many unresolved questions. Usually, the variational principle is applied to this equation in the standard, Dirac-Pauli, representation. All observables derived from the Dirac equation are invariant with respect to the choice of the representation (i.e. to a similarity transformation in the four-dimensional spinor space). However, in order to control the behavior of the variational energy, the trial functions are subjected to several conditions, as for example the kinetic balance condition. These conditions are usually representation-dependent. The aim of this work is an analysis of some consequences of this dependence. 

The Dirac-Coulomb-equation (i.e. the dimensionless equation with Coulomb potential) has exact solutions and can therefore be used as a good starting point for perturbation theory. 

The Dirac-Coulomb equation for a central potential has the form... 

Having discussed the eigenvalues and eigenfunctions of the Dirac-Coulomb equation in some detail, we are now going to scetch a possible method for find-... 

Hence the function ipn indeed gives the exponential decay described in (117). Finally, we find the solution of the Dirac-Coulomb equation with energy Cn,... 

For the relativistic case there are three analogous choices of expansion functions to those discussed above. The hydrogenic functions have their analogue in the L-spinors obtained from the solution of the Dirac-Coulomb equation [4]. Again their use is mainly restricted to analytic work in atomic calculations, due to the difficulties in evaluating the integrals [5]. The analogue of the STO is the S-spinor which may be written in the form... 

We now investigate the nrl and DPT for the Dirac Coulomb Hamiltonian. For the sake of simplicity we consider a two-electron system with the Dirac-Coulomb equation ... 

We could not show here the results of solving the relativistic Dirac-Coulomb equation. The FC method can be extended to the case of the Dirac-Coulomb equation with only a small modification [36]. It is important to use the inverse Dirac-Coulomb equation to circumvent the variational collapse problem which often appears in the relativistic calculations [37]. 

G. Pestka, M. Byhcki, J. Karwowski. Dirac-Coulomb Equation Playing with Artifacts. In S. Wilson, P. J. Grout, J. Maru-ani, G. Delgado-Barrio, P. Piecuch, Ed., Frontiers in Quantum Systems in Chemistry and Physics, p. 215. Springer, 2008. 

A. Rutkowski. Relativistic perturbation theory III. A new perturbation approach to the two-electron Dirac-Coulomb equation. /. Phys. B At. Mol. Opt. Phys., 19 (1986) 3443-3455. 

It should be noted that the two-electron term in this Dirac—Coulomb equation is based on a classical (i.e., nonrelativistic) picture of the interaction, and it is therefore not Lorentz invariant. In many applications this is a problem of minor importance, and results that are in good agreement with experiment often are obtained with the Dirac-Coulomb equation (Eqs. [71]—[74]) or with theory derived from it through further simplifications. For situations calling for a more accurate model, a relativistic picture of the electron—electron interaction is given by the Breit operator ... 

Heavy atoms exhibit large relativistic effects, often too large to be treated perturba-tively. The Schrodinger equation must be supplanted by an appropriate relativistic wave equation such as Dirac-Coulomb or Dirac-Coulomb-Breit. Approximate one-electron solutions to these equations may be obtained by the self-consistent-field procedure. The resulting Dirac-Fock or Dirac-Fock-Breit functions are conceptually similar to the familiar Hartree-Fock functions the Hartree-Fock orbitals are replaced, however, by four-component spinors. Correlation is no less important in the relativistic regime than it is for the lighter elements, and may be included in a similar manner. 

The relativistic many-electron Hamiltonian cannot be written in closed form it may be derived perturbatively from quantum electrodynamics [1]. The simplest form is the Dirac-Coulomb (DC) Hamiltonian, where the nonrelativistic one-electron terms in the Schrodinger equation are replaced by the one-electron Dirac operator hj). 

In this paper we present the first application of the ZORA (Zeroth Order Regular Approximation of the Dirac Fock equation) formalism in Ab Initio electronic structure calculations. The ZORA method, which has been tested previously in the context of Density Functional Theory, has been implemented in the GAMESS-UK package. As was shown earlier we can split off a scalar part from the two component ZORA Hamiltonian. In the present work only the one component part is considered. We introduce a separate internal basis to represent the extra matrix elements, needed for the ZORA corrections. This leads to different options for the computation of the Coulomb matrix in this internal basis. The performance of this Hamiltonian and the effect of the different Coulomb matrix alternatives is tested in calculations on the radon en xenon atoms and the AuH molecule. In the atomic cases we compare with numerical Dirac Fock and numerical ZORA methods and with non relativistic and full Dirac basis set calculations. It is shown that ZORA recovers the bulk of the relativistic effect and that ZORA and Dirac Fock perform equally well in medium size basis set calculations. For AuH we have calculated the equilibrium bond length with the non relativistic Hartree Fock and ZORA methods and compare with the Dirac Fock result and the experimental value. Again the ZORA and Dirac Fock errors are of the same order of magnitude. 

Equation (1) is obtained by using an expansion in E/ 2c - Vc) on the Dirac Fock equation. This expansion is valid even for a singular Coulombic potential near the nucleus, hence the name regular approximation. This is in contrast with the Pauli method, which uses an expansion in (E — V)I2(. Everything is written in terms of the two component ZORA orbitals, instead of using the large and small component Dirac spinors. This is an extra approximation with respect to the original formalism. 

EDE in the external Coulomb field in Fig. 1.6. The eigenfunctions of this equation may be found exactly in the form of the Dirac-Coulomb wave functions (see, e.g, [10]). For practical purposes it is often sufficient to approximate these exact wave functions by the product of the Schrodinger-Coulomb wave functions with the reduced mass and the free electron spinors which depend on the electron mass and not on the reduced mass. These functions are very convenient for calculation of the high order corrections, and while below we will often skip some steps in the derivation of one or another high order contribution from the EDE, we advise the reader to keep in mind that almost all calculations below are done with these unperturbed wave functions. 

By inserting the equations defining the kinetic energy operators and the pairwise interaction operators into Eq. (8) we obtain the Dirac-Coulomb-Breit Hamiltonian, which is in chemistry usually considered the fully relativistic reference Hamiltonian. 

From the four-component Dirac-Coulomb-Breit equation, the terms [99]—[102] can be deduced without assuming external fields. A Foldy-Wouthuysen transformation23 of the electron-nuclear Coulomb attraction and collecting terms to order v1 /c1 yields the one-electron part [99], Similarly, the two-electron part [100] of the spin-same-orbit operator stems from the transformation of the two-electron Coulomb interaction. The spin-other-orbit terms [101] and [102] have a different origin. They result, among other terms, from the reduction of the Gaunt interaction. 

A second possibility to obtain a solution of the Dirac Coulomb problem would be to solve Do e)u r) = 0. This differential equation is solved (for any e) by the singular ftmction u r) = Because of the singularity at... 

We introduce the change of the metric characteristic of DPT, and expand in powers of c. To 0(c ) we get the non-relativistic Hartree-Fock equations in Levy-Leblond form. The leading relativistic correction to the energy is then expressible in terms of nonrelativistic HF spin orbitals or rather the corresponding lower components xf - For the Dirac-Coulomb operator we get after some rearrangement [17, 18] ... 

Since the Dirac equation is valid only for the one-electron system, the one-electron Dirac Hamiltonian has to be extended to the many-electron Hamiltonian in order to treat the chemically interesting many-electron systems. The straightforward way to construct the relativistic many-electron Hamiltonian is to augment the one-electron Dirac operator, Eq. (70) with the Coulomb or Breit (or its approximate Gaunt) operator as a two-electron term. This procedure yields the Dirac-Coulomb (DC) or Dirac-Coulomb-Breit (DCB) Hamiltonian derived from quantum electrodynamics (QED)... 

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