On the universality of the long-/short-range separation in multiconfigurational density-functional theory

摘要

In many cases, the dynamic correlation can be calculated quite accurately and at a fairly low computational cost in Kohn-Sham density-functional theory (KS-DFT), using current standard approximate functionals. However, in general, KS-DFT does not treat static correlation effects (near degeneracy) adequately which, on the other hand, can be described in wave-function theory (WFT), for example, with a multiconfigurational self-consistent field (MCSCF) model. It is therefore of high interest to develop a hybrid model which combines the best of both WFT and DFT approaches. The merge of WFT and DFT can be achieved by splitting the two-electron interaction into long-range and short-range parts. The long-range part is then treated by WFT and the short-range part by DFT. In this work the authors consider the so-called "erf" long-range interaction erf(mu r(12))/r(12), which is based on the standard error function, and where mu is a free parameter which controls the range of the long-/short-range decomposition. In order to formulate a general method, they propose a recipe for the definition of an optimal mu(opt) parameter, which is independent of the approximate short-range functional and the approximate wave function, and they discuss its universality. Calculations on a test set consisting of He, Be, Ne, Mg, H-2, N-2, and H2O yield mu(opt)approximate to 0.4 a.u.. A similar analysis on other types of test systems such as actinide compounds is currently in progress. Using the value of 0.4 a.u. for mu, encouraging results are obtained with the hybrid MCSCF-DFT method for the dissociation energies of H-2, N-2, and H2O, with both short-range local-density approximation and PBE-type functionals. (c) 2007 American Institute of Physics.