An expansion of Hartree-Fock and correlation energies, relativistic corrections and the dipole matrix element in the powers of of 1/Z

Abstract

Feynman diagrammatic technique was used for the calculation of Hartree-Fock and correlation energies, relativistic corrections, dipole matrix element. The whole energy of atomic system was defined as a polen-electron Green function. Breit operator was used for the calculation of relativistic corrections. The Feynman diagrammatic technique was developed for 〈H_B>. Analytical expressions for the contributions from diagrams were received. The calculations were carried out for the terms of such configurations as 1s² 2sⁿ¹ 2pⁿ² (2 ≧n₁≧ 0, 6≧ n₂ ≧ 0). Numerical results are presented for the energies of the terms in the form

$$E = E_0 Z^2 + \Delta {\rm E}_2 + \frac{1}{Z}\Delta {\rm E}_3 + \frac{{\alpha ^2 }}{4}(E_0^r + \Delta {\rm E}_1^r Z^3 )$$

and for fine structure of the terms in the form

$$\begin{gathered} \left\langle {1s^2 2s^{n_1 } 2p^{n_2 } LSJ|H_B |1s^2 2s^{n_1 \prime } 2p^{n_2 \prime } L\prime S\prime J} \right\rangle = \hfill \\ = ( - 1)^{\alpha + S\prime + J} \left\{ {\begin{array}{*{20}c} {L S J} \\ {S\prime L\prime 1} \\ \end{array} } \right\}\frac{{\alpha ^2 }}{4}(Z - A)^3 [E^{(0)} (Z - B) + \varepsilon _{co} ] + \hfill \\ + ( - 1)^{L + S\prime + J} \left\{ {\begin{array}{*{20}c} {L S J} \\ {S\prime L\prime 2} \\ \end{array} } \right\}\frac{{\alpha ^2 }}{4}(Z - A)^3 \varepsilon _{cc} . \hfill \\ \end{gathered} $$

Dipole matrix elements are necessary for calculations of oscillator strengths and transition probabilities. For dipole matrix elements two members of expansion by 1/Z have been obtained. Numerical results were presented in the form P(a,a′) = a/Z(1+τ/Z).