Dual-hybrid direct random phase approximation and second-order screened exchange with nonlocal van der Waals...

We have added the nonlocal van der Waals correlation energy functional of Vydrov and Van Voorhis in 2010 (VV10NL) to the dual-hybrid direct random phase approximation (dRPA75) and second-order screened exchange (SOSEX75) for noncovalent interactions. The obtained methods are denoted as dRPA75-NL and SOSEX75-NL, and the corresponding short-range attenuation parameters are fitted with the large aug-cc-pV5Z basis set against the S66 dataset. Therefore, the dRPA75-NL method overcomes the error cancellation problem of the dRPA75 method with the relatively small aug-cc-pVTZ basis set for noncovalent interactions. Based on our benchmark computations, the dRPA75-NL and SOSEX75-NL methods perform very well on evaluating noncovalent interaction energies. Compared with the double-hybrid density functionals (DHDFs) of DSD-PBEP86-NL and DOD-PBEP86-NL, the dRPA75-NL and SOSEX75-NL methods perform much better on charge transfer interactions. Furthermore, the SOSEX75-NL method also gives insight into the development of computational methods for both closed-shell and open-shell noncovalent interactions. In summary, our computations demonstrate that even the full dRPA and SOSEX correlations still need additional dispersion corrections for noncovalent interactions.