Towards a systematic way to correct density functional approximations

Abstract

In order to simulate the exact universal density functional, approximations are nowadays constructed by permitting more flexibility in its ansatz. In view of the difficulty of defining a systematically improvable form for it, this paper argues that an alternative way could be considered. It falls within the class of hybrid functionals with multi-determinant wave functions. The parameter controlling the hybridization is considered as variable. The invariance of the exact result with respect to changes in this variable is used to introduce information about the system under consideration, and to correct the density functional result. The construction considered in this paper accelerates convergence from the model system to the physical one, in the vicinity of the latter. The method, at the present level of implementation, should be seen as a starting point for further development, and not necessarily as a computationally advantageous tool. © 2014 AIP Publishing LLC.