A second-quantization framework for the unified treatment of relativistic and nonrelativistic molecular perturbations by response theory

A formalism is presented for the calculation of relativistic corrections to molecular electronic energies and properties. After a discussion of the Dirac and Breit equations and their first-order Foldy-Wouthuysen [Phys. Rev. 78, 29 (1950)] transformation, we construct a second-quantization electronic Hamiltonian, valid for all values of the fine-structure constant alpha. The resulting alpha-dependent Hamiltonian is then used to set up a perturbation theory in orders of alpha(2), using the general framework of time-independent response theory, in the same manner as for geometrical and magnetic perturbations. Explicit expressions are given to second order in alpha(2) for the Hartree-Fock model. However, since all relativistic considerations are contained in the alpha-dependent Hamiltonian operator rather than in the wave function, the same approach may be used for other wave-function models, following the general procedure of response theory. In particular, by constructing a variational Lagrangian using the alpha-dependent electronic Hamiltonian, relativistic corrections can be calculated for nonvariational methods as well. (c) 2006 American Institute of Physics.