Fourier–Legendre expansion of the one-electron density matrix of ground-state two-electron atoms.

The density matrix ρ(r,r′) of a spherically symmetric system can be expanded as a Fourier–Legendre series of Legendre polynomials Pl(cos θ=r·r′/rr′). Application is here made to harmonically trapped electron pairs (i.e., Moshinsky’s and Hooke’s atoms), for which exact wavefunctions are known, and to the helium atom, using a near-exact wavefunction. In the present approach, generic closed form expressions are derived for the series coefficients of ρ(r,r′). The series expansions are shown to converge rapidly in each case, with respect to both the electron number and the kinetic energy. In practice, a two-term expansion accounts for most of the correlation effects, so that the correlated density matrices of the atoms at issue are essentially a linear functions of Pl(cos θ)=cos θ. For example, in the case of Hooke’s atom, a two-term expansion takes in 99.9% of the electrons and 99.6% of the kinetic energy. The correlated density matrices obtained are finally compared to their determinantal counterparts, using a simplified representation of the density matrix ρ(r,r′), suggested by the Legendre expansion. Interestingly, two-particle correlation is shown to impact the angular delocalization of each electron, in the one-particle space spanned by the r and r′ variables. [ABSTRACT FROM AUTHOR]