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Noncovalent Interactions from Models for the Moller-Plesset Adiabatic Connection.

ABSTRACT: Given the omnipresence of noncovalent interactions (NCIs), their accurate simulations are of crucial importance across various scientific disciplines. Here we construct accurate models for the description of NCIs by an interpolation along the Møller-Plesset adiabatic connection (MP AC). Our interpolation approximates the correlation energy, by recovering MP2 at small coupling strengths and the correct large-coupling strength expansion of the MP AC, recently shown to be a functional of the Hartree-Fock density. Our models are size consistent for fragments with nondegenerate ground states, have the same cost as double hybrids, and require no dispersion corrections to capture NCIs accurately. These interpolations greatly reduce large MP2 errors for typical π-stacking complexes (e.g., benzene-pyridine dimers) and for the L7 data set. They are also competitive with state-of-the-art dispersion enhanced functionals and can even significantly outperform them for a variety of data sets, such as CT7 and L7.

SUBMITTER: Daas TJ

PROVIDER: S-EPMC8280728 | biostudies-literature | 2021 May

REPOSITORIES: biostudies-literature

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Noncovalent Interactions from Models for the Møller-Plesset Adiabatic Connection.

Daas Kimberly J KJ Fabiano Eduardo E Della Sala Fabio F Gori-Giorgi Paola P Vuckovic Stefan S

The journal of physical chemistry letters 20210518 20

Given the omnipresence of noncovalent interactions (NCIs), their accurate simulations are of crucial importance across various scientific disciplines. Here we construct accurate models for the description of NCIs by an interpolation along the Møller-Plesset adiabatic connection (MP AC). Our interpolation approximates the correlation energy, by recovering MP2 at small coupling strengths and the correct large-coupling strength expansion of the MP AC, recently shown to be a functional of the Hartre ...[more]

PMID: 34003655

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Project description:This work systematically assesses the influence of reference orbitals, regularization, and scaling on the performance of second- and third-order Møller-Plesset perturbation theory wave function methods for noncovalent interactions (NCIs). Testing on 19 data sets (A24, DS14, HB15, HSG, S22, X40, HW30, NC15, S66, AlkBind12, CO2Nitrogen16, HB49, Ionic43, TA13, XB18, Bauza30, CT20, XB51, and Orel26rad) covers a wide range of different NCIs including hydrogen bonding, dispersion, and halogen bonding. Inclusion of potential energy surfaces from different hydrogen bonds and dispersion-bound complexes gauges accuracy for nonequilibrium geometries. Fifteen methods are tested. In notation where nonstandard choices of orbitals are denoted as methods:orbitals, these are MP2, κ-MP2, SCS-MP2, OOMP2, κ-OOMP2, MP3, MP2.5, MP3:OOMP2, MP2.5:OOMP2, MP3:κ-OOMP2, MP2.5:κ-OOMP2, κ-MP3:κ-OOMP2, κ-MP2.5:κ-OOMP2, MP3:ωB97X-V, and MP2.5:ωB97X-V. Furthermore, we compare these methods to the ωB97M-V and B3LYP-D3 density functionals, as well as CCSD. We find that the κ-regularization (κ = 1.45 au was used throughout) improves the energetics in almost all data sets for both MP2 (in 17 out of 19 data sets) and OOMP2 (16 out of 19). The improvement is significant (e.g., the root-mean-square deviation (RMSD) for the S66 data set is 0.29 kcal/mol for κ-OOMP2 versus 0.67 kcal/mol for MP2) and for interactions between stable closed-shell molecules, not strongly dependent on the reference orbitals. Scaled MP3 (with a factor of 0.5) using κ-OOMP2 reference orbitals (MP2.5:κ-OOMP2) provides significantly more accurate results for NCIs across all data sets with noniterative O(N6) scaling (S66 data set RMSD: 0.10 kcal/mol). Across the entire data set of 356 points, the improvement over standard MP2.5 is approximately a factor of 2: RMSD for MP3:κ-OOMP2 is 0.25 vs 0.50 kcal/mol for MP2.5. The use of high-quality density functional reference orbitals (ωB97X-V) also significantly improves the results of MP2.5 for NCI over a Hartree-Fock orbital reference. All our assessments and conclusions are based on the use of the medium-sized aug-cc-pVTZ basis to yield results that are directly compared against complete basis set limit reference values.

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Noncovalent Interactions from Models for the Moller-Plesset Adiabatic Connection.

Publications

Noncovalent Interactions from Models for the Møller-Plesset Adiabatic Connection.

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