Open AccessRegularized Second-Order Møller–Plesset Theory: A More Accurate Alternative to Conventional MP2 for Noncovalent Interactions and Transition Metal Thermochemistry for the Same Computational Cost
Author(s) -
James Shee,
Matthias Loipersberger,
Adam Rettig,
Joonho Lee,
Martin HeadGordon
Publication year - 2021
Publication title -
the journal of physical chemistry letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.563
H-Index - 203
ISSN - 1948-7185
DOI - 10.1021/acs.jpclett.1c03468
Subject(s) - thermochemistry , regularization (linguistics) , statistical physics , chemistry , computational chemistry , transition metal , non covalent interactions , thermodynamics , molecule , physics , computer science , hydrogen bond , organic chemistry , artificial intelligence , catalysis
Second-order Møller-Plesset theory (MP2) notoriously breaks down for π-driven dispersion interactions and dative bonds in transition metal complexes. Herein, we investigate three physically justified forms of single-parameter, energy-gap dependent regularization which can yield high and transferable accuracy for a variety of noncovalent interactions (including S22, S66, and L7 test sets) and (mostly closed shell) transition metal thermochemistry. Regularization serves to damp overestimated pairwise additive contributions, renormalizing first-order amplitudes such that the effects of higher-order correlations are incorporated. The optimal parameter values for the noncovalent and transition metal sets are 1.1, 0.7, and 0.4 for κ, σ, and σ 2 regularizers, respectively. However, such regularization slightly degrades the accuracy of conventional MP2 for some small-molecule test sets, most of which have relatively large average frontier energy gaps. Our results suggest that appropriately regularized MP2 models may improve double hybrid density functionals, at no additional cost over conventional MP2.