Coulomb-Dirac function

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. 

A more precise value than in [63] of the nonlogarithmic correction of order a Za) for the IS -state was obtained in [66, 67], with the help of a specially developed perturbation theory for the Dirac-Coulomb Green function which expressed this function in terms of the nonrelativistic Schrodinger-Coulomb Green function [68, 69]. But the real breakthrough was achieved in [70, 71], where a new very effective method of calculation was suggested and very precise values of the nonlogarithmic corrections of order a Zo) for the IS -and 25-states were obtained. We will briefly discuss the approach of papers [70, 71] in the next subsection. 

In the Schrodinger-Coulomb approximation the expression in (6.33) reduces to the leading nuclear size correction in (6.3). New results arise if we take into account Dirac corrections to the Schrodinger-Coulomb wave functions of relative order (Za). For the nS states the product of the wave functions in (6.33) has the form (see, e.g, [17])... 

The leading electron polarization contribution in (7.7) was calculated in the nonrelativistic approximation between the Schrodinger-Coulomb wave functions. Relativistic corrections of relative order (Za) to this contribution may easily be obtained in the nonrecoil limit. To this end one has to calculate the expectation value of the radiatively corrected potential in (7.1) between the relativistic Coulomb-Dirac wave functions instead of averaging it with the nonrelativistic Coulomb-Schrodinger wave functions. 

The binding corrections to h q)erfine splitting as well as the main Fermi contribution are contained in the matrix element of the interaction Hamiltonian of the electron with the external vector potential created by the muon magnetic moment (A = V X /Lx/(47rr)). This matrix element should be calculated between the Dirac-Coulomb wave functions with the proper reduced mass dependence (these wave functions are discussed at the end of Sect. 1.3). Thus we see that the proper approach to calculation of these corrections is to start with the EDE (see discussion in Sect. 1.3), solve it with the convenient... 

The logarithmic nuclear size correction of order Za) EF may simply be obtained from the Zemach correction if one takes into account the Dirac correction to the Schrodinger-Coulomb wave function in (3.65) [7]... 

R. Szmytkowski. The Dirac-Coulomb Sturmians and the Series Expansion of the Dirac-Coulomb Green Functions Application to the Relativistic Polarizability of the Hydrogen Like Atoms. /. Phys. B At. Mol Opt. Phys., 30 (1997) 825-861. 

For tiie case of a Coulomb field, special methods exist that reduce the equation to a form where the nonrelativistic solutions can be used.11 Thus, if we denote by tji the wave function of the electron moving in a Coulomb field, then t/i obeys the Dirac equation... 

Co-representation matrices explicit forms, 733 multiplication of, 731 of the nonunitary group, 732 Corliss, L. M., 757 Corson, E. M., 498 Coulomb field Dirac equation in, 637 Coulomb gauge, 643,657,664 Counting functions, 165 Covariance matrix, 160 Covariant amplitude of one-particle system, 511 of one, two, etc. particle systems, 511... 

Fig. 1. BLYP/uncDZ mean dipole polarizability of the mercury atom as a function of frequency. All values in atomic units. SR+SO refers to calculations based on the Dirac-Coulomb Hamiltonians, whereas SR refers to calculations in which all spin-orbit interaction has been eliminated.

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. 

An application of the variational principle to an unbounded from below Dirac-Coulomb eigenvalue problem, requires imposing upon the trial function certain conditions. Among these the most important are the symmetry properties, the asymptotic behaviour and the relations between the large and the small components of the wavefunction related to the so called kinetic balance [1,2,3]. In practical calculations an exact fulfilment of these conditions may be difficult or even impossible. Therefore a number of minimax principles [4-7] have been formulated in order to allow for some less restricted choice of the trial functions. There exist in the literature many either purely intuitive or derived from computational experience, rules which are commonly used as a guidance in generating basis sets for variational relativistic calculations. 

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. 

---