On the use of Slater-type spinor orbitals in Dirac-Hartree-Fock method. Results for hydrogen-like atoms with super$-$critical nuclear charge

Abstract: This work presents the formalism for evaluating molecular SCF equations, as adapted to four$-$component Dirac spinors, which in turn reduce to Slater$-$type orbitals with non$-$integer principal quantum numbers in the non$-$relativistic limit. The "catastrophe" which emerges for a charge numbers $Z>137$, in solving the Dirac equation with a potential corresponding to a point$-$charge is avoided through using Slater$-$type spinor orbitals in the algebraic approximation. It is observed that, ground$-$state energy of hydrogen$-$like atoms reaches the negative$-$energy continuum $\left(-mc^2 \right)$ while critical nuclear charge $Z_{c}$, about $Z_{c}=160$. The difficulty associated with finding relations for molecular integrals over Slater$-$type spinors which are not$-$analytic in the sense of complex analysis at $r = 0$, is eliminated. Unique numerical accuracy is provided by solving the molecular integrals through Laplace expansion of Coulomb interaction and prolate spheroidal coordinates. New convergent series representation formulae are derived. The technique draws on previous work by the author and the general formalism is presented in this paper.