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The Performance of Dunning, Jensen and Karlsruhe Basis Sets on Computing Relative Energies and Geometries

  • In an effort to assist researchers in choosing basis sets for quantum mechanical modeling of molecules (i.e. balancing calculation cost versus desired accuracy), we present a systematic study on the accuracy of computed conformational relative energies and their geometries in comparison to MP2/CBS and MP2/AV5Z data, respectively. In order to do so, we introduce a new nomenclature to unambiguously indicate how a CBS extrapolation was computed. Nineteen minima and transition states of buta-1,3-diene, propan-2-ol and the water dimer were optimized using forty-five different basis sets. Specifically, this includes one Pople (i.e. 6-31G(d)), eight Dunning (i.e. VXZ and AVXZ, X=2-5), twenty-five Jensen (i.e. pc-n, pcseg-n, aug-pcseg-n, pcSseg-n and aug-pcSseg-n, n=0-4) and nine Karlsruhe (e.g. def2-SV(P), def2-QZVPPD) basis sets. The molecules were chosen to represent both common and electronically diverse molecular systems. In comparison to MP2/CBS relative energies computed using the largest Jensen basis sets (i.e. n=2,3,4), the use of smaller sizes (n=0,1,2 and n=1,2,3) provides results that are within 0.11--0.24 and 0.09-0.16 kcal/mol. To practically guide researchers in their basis set choice, an equation is introduced that ranks basis sets based on a user-defined balance between their accuracy and calculation cost. Furthermore, we explain why the aug-pcseg-2, def2-TZVPPD and def2-TZVP basis sets are very suitable choices to balance speed and accuracy.

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Document Type:Preprint
Author:Karl Kirschner, Dirk Reith, Wolfgang Heiden
Parent Title (English):ChemRxiv
Edition:Version 2
First Page:1
Last Page:24
Publisher:American Chemical Society ACS
Publishing Institution:Hochschule Bonn-Rhein-Sieg
Date of first publication:2019/12/20
Publication status:Published paper in: Soft Materials, https://doi.org/10.1080/1539445X.2020.1714656
Funding Information:Computer hardware was supported by the Federal Ministry for Education and Research and by the Ministry for Innovation, Science, Research, and Technology of the state Northrhine-Westfalia (research grant 13FH156IN6).
Departments, institutes and facilities:Fachbereich Informatik
Fachbereich Elektrotechnik, Maschinenbau und Technikjournalismus
Projects:EI-HPC - Enabling Infrastructure for HPC-Applications (DE/BMBF/13FH156IN6)
Dewey Decimal Classification (DDC):5 Naturwissenschaften und Mathematik / 54 Chemie / 540 Chemie und zugeordnete Wissenschaften
Entry in this database:2019/12/11
Licence (German):License LogoCreative Commons - CC BY-NC-ND - Namensnennung - Nicht kommerziell - Keine Bearbeitungen 4.0 International