AbstractThe local density approximation (LDA) to the exchange potential Vx(r), namely the ρ1/3 electron gas form, was already transcended in Slater's 1951 paper. Here, using Dirac's 1930 form for the exchange energy density ϵx(r), the Slater (Sl) nonlocal exchange potential V(r) is defined by 2ϵx(r)/ρ(r). In spherical atomic ions, say the Be or Ne‐like series, this form V(r) already has the correct behavior in both r → 0 and r → ∞ limits when known properties of the exchange energy density ϵx(r) and the ground‐state electron density ρ(r) are invoked. As examples, some emphasis will first be given to the use of the so‐called 1/Z expansion in such spherical atomic ions, for which analytic results can be obtained for both ϵx(r) and ρ(r) as the atomic number Z becomes large. The usefulness of the 1/Z expansion is directly demonstrated for the U atomic ion with 18 electrons by comparison with the optimized effective potential prediction. A rather general integral equation for the exchange potential is then proposed. Finally, without appeal to large Z, two‐level systems are considered, with specific reference to the Be atom and to the LiH molecule. In all cases treated, the Slater potential V(r) is a valuable starting point, even though it needs appreciable quantitative corrections reflecting directly atomic shell structure. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005