Accuracy of Intermolecular interaction Energies, Particularly Those of Hetero Atom Containing Molecules Obtained by van der Waals DFT Calculations. Issue 6 (6th February 2023)

• Record Type: Journal Article
• Authors: Tsuzuki, Seiji; Kaneko, Tomoaki; Sodeyama, Keitaro
• Is Part Of: ChemistrySelect. Volume 8:Issue 6(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2023-02-06
• Subjects: Calculation accuracy -- Density functional calculations -- Dispersion interaction -- Noncovalent interactions -- vdW Functionals; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202203754
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: The performance of 24 vdW‐DF functionals were evaluated. The calculated intermolecular interaction potentials for 11 complexes, which conatain O, S, Se, N, P, F, Cl and Br atoms, were compared with CCSD(T)/CBS level potentials to evaluate their accuracy. The performance depends on the choice of vdW‐functional significantly. The vdW‐DF3‐opt1 functional shows the best performance. The deviation ratios of calculated interaction energies of the complexes using the vdW‐DF3‐opt1 functional to CCSD(T) level interaction energies at the potential minima are −6 to 14 %. As a general tendency, the accuracy is improved in the order of vdW‐DF, vdW‐DF2, and vdW‐DF3, but even if they belong to the same group, the accuracy greatly differs depending on each functional. The calculations of hydrocarbon molecules show better performance compared with heteroatom containing molecules in most cases. The calculations using the vdW‐DF3‐opt1 functional and the best dispersion corrected DFT calculations show nearly identical performance. Abstract : The intermolecular interaction potentials of 11 complexes obtained by vdW‐DFT calculations using 24 functionals show that the calculated potentials depend strongly on the choice of functionals. The vdW‐DF3‐opt1 functional shows the best performance among the 24 functionals. Intermolecular interaction potential for furan dimer obtained using the vdW‐DF3‐opt1 is close to CCSD(T) level potential as shown.