Expectation values in two-component relativistic theories

We examined numerically the equivalence between the expectation values calculated by the four-component wave function and those calculated by the two-component wave functions generated by the infinite-order Douglas-Kroll (IODK) transformation. We showed the expectation values < r(-1)> and in several closed-shell atoms using the so-called picture-changed 2 x 2 operators at some levels of approximation. The effect of the two-electron Coulomb term was also discussed. The numerical results indicated that the accuracy of < r(-1)> mainly depends on the level of the wave functions, while that of is affected by the accuracy of both the wave functions and the picture-changed operators. As expected, the picture-changed operators and the IODK wave functions generate essentially equivalent expectation values in comparison with those calculated by the four-component Dirac-type method. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3397070]