Two-Electron Systems and the Breit Equation

Presentations of the semi-classical theory are rare. The textbook by Mott and Sneddon [169] from 1948 is an example where this has been attempted in some detail, although — after having derived the quantum mechanical energy expression for the retarded electromagnetic interaction of two electrons — the authors come to the conclusion that... it loill he appreciated that the derivation does not depend on any very consecutive argument [169, p. 339]. In the following we will see that the situation is actually not that bad. 

The first step toward a practical relativistic many-electron theory in the molecular sciences is the investigation of the two-electron problem in an external field which we meet, for instance, in the helium atom. Salpeter and Bethe derived a relativistic equation for the two-electron bound-state problem [135,170-173] rooted in quantum electrod)mamics, which features two separate times for the two particles. If we assume, however, that an absolute time is a good approximation, we arrive at an equation first considered by Breit [101,174,175]. The Bethe-Salpeter equation as well as the Breit equation hold for a 16-component wave function. From a formal point of view, these 16 components arise when the two four-dimensional one-electron Hilbert spaces are joined by direct multiplication to yield the two-electron Hilbert space. 

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In the previous two sections, we have presented the Breit-Pauli perturbation Hamiltonian for one- and two-electron relativistic corrections of order 1/c to the nonrelativistic Hamiltonian. But there is a problem for many-electron systems. For the perturbation theory to be valid, the reference wave function must be an eigenfunction of the zeroth-order Hamiltonian. If we take this to be the nonrelativistic Hamiltonian and the perturbation parameter to be 1/c, we do not have the exact solutions of the zeroth-order equation. 

For the computational investigation of molecular systems containing heavy atoms, such as transition metals, lanthanides, and actinides, we could neglect neither relativity nor electron correlation. Relativistic effects, both spin-free and spin-orbit, increase with the nuclear charge of atoms. Therefore, instead of the nonrelativistic Schrodinger equation, we must start with the Dirac equation, which has four-component solutions. For many-electron systems, the four-component Hamiltonian is constructed from the one-electron Dirac operator with an approximated relativistic two-electron operator, such as the Coulomb, Breit, or Gaunt operator, within the nopair approximation. The four-component method is relativistically rigorous, which includes both spin-free and spin-orbit effects in a balanced way. However it requires much computational time since it contains more variational parameters than the approximated, one or two-component method. 

Here Hd, is the Dirac Hamiltonian for a single particle, given by Eq. [30]. Recall from above that the Coulomb interaction shown is not strictly Lorentz invariant therefore, Eq. [59] is only approximate. The right-hand side of the equation gives the relativistic interactions between two electrons, and is called the Breit interaction. Here a, and a, denote Dirac matrices (Eq. [31]) for electrons i and /. Equation [59] can be cast into equations similar to Eq. [36] for the Foldy-Wouthuysen transformation. After a sequence of unitary transformations on the Hamiltonian (similar to Eqs. [37]-[58]) is applied to reduce the off-diagonal contributions, one obtains the Hamiltonian in terms of commutators, similar to Eq. [58]. When each term of the commutators are expanded explicitly, one arrives at the Breit-Pauli Hamiltonian, for a many-electron system " ... 

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