Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: A path toward chemical accuracy
2021
Second-order Moller-Plesset perturbation theory (MP2) provides a valuable alternative to density functional
theory for modeing problems in organic and biological chemistry. However, MP2 suffers from known lim-
itations in the description of van der Waals dispersion interactions and reaction thermochemistry. Here,
a spin-component-scaled, dispersion-corrected MP2 model (SCS-MP2D) is proposed that addresses these
weaknesses. The dispersion correction, which is based on Grimme’s D3 formalism, replaces the uncoupled
Hartree-Fock dispersion inherent in MP2 with a more robust coupled Kohn-Sham treatment. The spin-
component scaling of the residual MP2 correlation energy then reduces the remaining errors in the model.
This two-part correction strategy solves the problem found in earlier spin-component-scaled MP2 models
where completely different spin-scaling parameters were needed for describing reaction energies versus in-
termolecular interactions. Results on 18 benchmark data sets and two challenging potential energy curves
demonstrate that SCS-MP2D considerably improves upon the accuracy of MP2 for intermolecular interac-
tions, conformational energies, and reaction energies. Its accuracy and computational cost are competitive
with state-of-the-art density functionals such as DSD-BLYP-D3(BJ), revDSD-PBEP86-D3(BJ), ωB97X-V,
and ωB97M-V for systems with ∼100 atoms.
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