Electron-pair momentum densities of heavy atoms Cs through Lr

Abstract

Spherically averaged electron-pair intracule (relative motion) h̄(v) and extracule (center-of-mass motion) d̄(P) densities in momentum space are constructed for the 49 heavy atoms Cs (atomic number Z=55) through Lr(Z=103), by using the numerical Hartree–Fock method. As known for the 53 lighter atoms from He(Z=2) to Xe(Z=54), the electron-pair densities h̄(v) and d̄(P) of the heavy atoms are found to be classified into three and two types, respectively, based on their modalities. No new types are observed even when f subshells are occupied. Subshell-pair analysis clarifies that different modalities reflect different valence electron configurations. The intracule 〈vn〉 and extracule 〈Pn〉 moments and the electron–electron coalescence h̄(0) and counterbalance d̄(0) densities are also obtained. The present results for Z=55–103, together with the previous ones [J. Chem. Phys. 107, 8510 (1997); 108, 3424 (1998)] for Z=2–54, provide a compilation of accurate Hartree–Fock values of the momentum-space electron-pair properties for the 102 neutral atoms in the periodic table.