Approximate exchange–correlation functionals built by modeling in a nonlinear way the adiabatic connection (AC) integrand of density functional theory have many attractive features, being virtually parameter-free and satisfying different exact properties, but they also have a fundamental flaw: they violate the size-consistency condition, crucial to evaluate interaction energies of molecular systems. We show that size consistency in the AC-based functionals can be restored in a very simple way at no extra computational cost. Results on a large set of benchmark molecular interaction energies show that functionals based on the interaction strength interpolation approximations are significantly more accurate than second-order perturbation theory.
American Chemical Society
22 May 2018
Volume: 9 Issue: 11 Pages: 3137-3142
The journal of physical chemistry letters