The origin of relativistic effects of atomic orbitals

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Abstract
A(R)= integral R0 ( integral psi a psi d Omega )r2 dr curves are presented for different contributions a to the energy of atomic orbitals. While all radial shells contribute about equally to the non-relativistic kinetic and potential orbital energies, there is almost perfect cancellation of these energies in the inner shells, and the total energy of an orbital is almost solely determined by its outermost shell. In contrast to this, the first-order relativistic mass-velocity, Darwin and spin-orbit energies originate from the innermost shells only, while all radial shells contribute to the so-called indirect relativistic orbital energy correction,. The indirect effect is important also for s atomic orbitals except for the central columns of the periodic system, where the indirect destabilisation is compensated by indirect stabilisation. This explains the 'gold maximum' of relativistic corrections.