Performance of the OP correlation functional in relation to its formulation: Influence of the exchange component and the effect of incorporating same-spin correlations.

Abstract

In the present study, we have investigated two significant features of the OP correlation functional, namely the incorporation of the exchange functional into itself, and the inclusion of only opposite-spin (OS) effects. To explore the latter feature, we have compared OP with B95 and a new functional introduced in the present study - the OPB method that combines OP with the same-spin (SS) component of B95. In general, we find that B95 and OPB perform comparably. Our comparisons of the various DFT procedures suggest that the incorporation of a meta-GGA (e.g., TPSS) into OP and OPB does not necessarily lead to a chemically more accurate procedure than the use of a related GGA (e.g., PBE). An important finding is the more notable (and somewhat more consistent) improvement in performance with the incorporation of SS correlation, particularly for longer-range chemical properties. Nonetheless, on average across our test sets of over 800 systems, the difference between the performances of OP versus B95 or OPB is not exceedingly large. By drawing a parallel between these DFT methods and the wavefunction scaled-MP2-type methods, we reason that one can further develop the OP functional, and perhaps a wider range of correlation functionals by combining it with the technique of range separation.