English

Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections

Chemical Physics 2021-06-10 v3

Abstract

For revDSD double hybrids, the G\"orling-Levy second-order perturbation theory component is an Achilles' Heel when applied to systems with significant near-degeneracy ("static") correlation. We have explored its replacement by the direct random phase approximation (dRPA), inspired by the SCS-dRPA75 functional of K\'allay and coworkers. The addition to the final energy of both a D4 empirical dispersion correction, and of a semilocal correlation component lead, to significant improvements, with DSD-PBEdRPA75-D4 approaching the performance of revDSD-PBEP86-D4 and the Berkeley ω\omegaB97M(2). This form appears to be fairly insensitive to the choice of semilocal functional, but does exhibit stronger basis set sensitivity than the PT2-based double hybrids (due to much larger prefactors for the nonlocal correlation). As an alternative, we explored adding an MP3-like correction term (in a medium-sized basis sets) to a range-separated ω\omegaDSD-PBEP86-D4 double hybrid, and found it to have significantly lower WTMAD2 (weighted mean absolute deviation) for the large and chemically diverse GMTKN55 benchmark suite; the added computational cost can be mitigated through density fitting techniques.

Keywords

Cite

@article{arxiv.2102.04943,
  title  = {Exploring Avenues Beyond Revised DSD Functionals: II. Random-Phase Approximation and scaled MP3 corrections},
  author = {Golokesh Santra and Emmanouil Semidalas and Jan M. L. Martin},
  journal= {arXiv preprint arXiv:2102.04943},
  year   = {2021}
}

Comments

J. Phys. Chem. A 125, ASAP (2021) Creative Commons License

R2 v1 2026-06-23T22:59:17.053Z