On the large interelectronic distance behavior of the correlation factor for explicitly correlated wave functions

Abstract

In currently most popular explicitly correlated electronic structure theories, the dependence of the wave function on the interelectronic distance rij is built via the correlation factor f (rij). While the short-distance behavior of this factor is well understood, little is known about the form of f (rij) at large rij. In this work, we investigate the optimal form of f (r12) on the example of the helium atom and helium-like ions and several well-motivated models of the wave function. Using the Rayleigh-Ritz variational principle, we derive a differential equation for f (r12) and solve it using numerical propagation or analytic asymptotic expansion techniques. We found that for every model under consideration, f (r12) behaves at large rij as r12ρeBr12 and obtained simple analytic expressions for the system dependent values of ρ and B. For the ground state of the helium-like ions, the value of B is positive, so that f (r12) diverges as r 12 tends to infinity. The numerical propagation confirms this result. When the Hartree-Fock orbitals, multiplied by the correlation factor, are expanded in terms of Slater functions rne-βr, n = 0,.,N, the numerical propagation reveals a minimum in f (r12) with depth increasing with N. For the lowest triplet state, B is negative. Employing our analytical findings, we propose a new "range-separated" form of the correlation factor with the short- and long-range r12 regimes approximated by appropriate asymptotic formulas connected by a switching function. Exemplary calculations show that this new form of f (r12) performs somewhat better than the correlation factors used thus far in the standard R12 or F12 theories. © 2013 AIP Publishing LLC.