Accurate non-covalent interactions from models for the Møller-Plesset adiabatic connection*

A range of failures of the second-order Mo̷ller−Plesset  perturbation theory (MP2) for noncovalent interactions (NCI) have been described in the literature [1,2]. Moreover, the whole MP series can be diverging for large non-covalent complexes [1]. Our model based on the Møller-Plesset (MP) adiabatic connection [3-5] fixes all these issues of MP2 at no extra cost [6]. In this talk, I will give a theoretical basis for these models, show results for specific classes of NCI complexes, and discuss strategies for further improvements.

[1] Nguyen BD, Chen GP, Agee MM, Burow AM, Tang MP, Furche F., Journal of chemical theory and computation. 2020 Feb 27;16(4):2258-73.

[2] Vuckovic S, Fabiano E, Gori-Giorgi P, Burke K. MAP: an MP2 accuracy predictor for weak interactions from adiabatic connection theory. Journal of chemical theory and computation. 2020 May 7;16(7):4141-9.

[3] Vuckovic S, Gori-Giorgi P, Della Sala F, Fabiano E. Restoring size consistency of approximate functionals constructed from the adiabatic connection. The journal of physical chemistry letters. 2018 May 22;9(11):3137-42.

[4] Seidl M, Giarrusso S, Vuckovic S, Fabiano E, Gori-Giorgi P. Communication: Strong-interaction limit of an adiabatic connection in Hartree-Fock theory. The Journal of chemical physics. 2018 Dec 28;149(24):241101.

[5] Daas TJ, Grossi J, Vuckovic S, Musslimani ZH, Kooi DP, Seidl M, Giesbertz KJ, Gori-Giorgi P. Large coupling-strength expansion of the Møller–Plesset adiabatic connection: From paradigmatic cases to variational expressions for the leading terms. The Journal of Chemical Physics. 2020 Dec 7;153(21):214112.

[6] Daas TJ, Fabiano E, Della Sala F, Gori-Giorgi P, Vuckovic S. Noncovalent Interactions from Models for the Møller–Plesset Adiabatic Connection. The journal of physical chemistry letters. 2021 May 18;12:4867-75.