A first-principles-based correlation functional for harmonious connection of short-range correlation and long-range dispersion

作者：Modrzejewski Marcin^*; Lesiuk Michal; Rajchel Lukasz; Szczesniak Malgorzata M; Chalasinski Grzegorz

来源：Journal of Chemical Physics, 2012, 137(20): 204121.

DOI：10.1063/1.4768228

We present a physically motivated correlation functional belonging to the meta-generalized gradient approximation (meta-GGA) rung, which can be supplemented with long-range dispersion corrections without introducing double-counting of correlation contributions. The functional is derived by the method of constraint satisfaction, starting from an analytical expression for a real-space spin-resolved correlation hole. The model contains a position-dependent function that controls the range of the interelectronic correlations described by the semilocal functional. With minimal empiricism, this function may be adjusted so that the correlation model blends with a specific dispersion correction describing long-range contributions. For a preliminary assessment, our functional has been combined with an atom-pairwise dispersion correction and full Hartree-Fock (HF)-like exchange. Despite the HF-exchange approximation, its predictions compare favorably with reference interaction energies in an extensive set of non-covalently bound dimers.

• 出版日期2012-11-28