Spin-component-scaled and dispersion-corrected second-order Møller-Plesset perturbation theory: a path toward chemical accuracy

• Published in: Physical chemistry chemical physics : PCCP 2022-02, Vol.24 (6), p.3695-3712
• Main Authors: Greenwell, Chandler, ezá, Jan, Beran, Gregory J. O
• Format: Article
• Language: English
• Subjects: Accuracy; Density functional theory; Dispersion; Perturbation theory; Potential energy; Thermochemistry
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/d1cp04922d

Second-order Møller-Plesset perturbation theory (MP2) provides a valuable alternative to density functional theory for modeling problems in organic and biological chemistry. However, MP2 suffers from known limitations in the description of van der Waals (London) 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 intermolecular 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 interactions, 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. Dispersion-corrected, spin-component-scaled second-order Møller-Plesset perturbation theory (SCS-MP2D) provides accuracy and computational efficiency that is competitive with high-quality density functionals.