New quantum number for the many-electron Dirac-Coulomb Hamiltonian

摘要

By breaking the spin symmetry in the relativistic domain, a powerful tool in physical sciences was lost. In this work, we examine an alternative of spin symmetry for systems described by the many-electron Dirac-Coulomb Hamiltonian. We show that the square of many-electron operator K+, defined as a sum of individual single-electron time-reversal (TR) operators, is a linear Hermitian operator which commutes with the Dirac-Coulomb Hamiltonian in a finite Fock subspace. In contrast to the square of a standard unitary many-electron TR operator K, the K-+(2) has a rich eigenspectrum having potential to substitute spin symmetry in the relativistic domain. We demonstrate that K+ is connected to K through an exponential mapping, in the same way as spin operators are mapped to the spin rotational group. Consequently, we call K+ the generator of the many-electron TR symmetry. By diagonalizing the operator K-+(2) in the basis of Kramers-restricted Slater determinants, we introduce the relativistic variant of configuration state functions (CSF), denoted as Kramers CSF. A new quantum number associated with K-+(2) has potential to be used in many areas, for instance, (a) to design effective spin Hamiltonians for electron spin resonance spectroscopy of heavy-element containing systems; (b) to increase efficiency of methods for the solution of many-electron problems in relativistic computational chemistry and physics; (c) to define Kramers contamination in unrestricted density functional and Hartree-Fock theory as a relativistic analog of the spin contamination in the nonrelativistic domain.