The performance of Dunning, Jensen, and Karlsruhe basis sets on computing relative energies and geometries. Issue 2 (2nd July 2020)

• Record Type: Journal Article
• Authors: Kirschner, Karl N.; Reith, Dirk; Heiden, Wolfgang
• Is Part Of: Soft materials. Volume 18:Issue 2-3(2020)
• Page Start: 200
• Page End: 214
• Publication Date: 2020-07-02
• Subjects: Basis set -- complete basis set limit -- water dimer -- propan-2-ol -- mp2; Materials science -- Periodicals; 620.11
• DOI: 10.1080/1539445X.2020.1714656
• Languages: English
• ISSNs: 1539-445X

Abstract

ABSTRACT: 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 45 different basis sets. Specifically, this includes one Pople (i.e. 6-31G(d)), 8 Dunning (i.e. VXZ and AVXZ, X = 2–5), 25 Jensen (i.e. pc-n, pcseg-n, aug-pcseg-n, pcSseg-n, and aug-pcSseg-n, n = 0–4), and 9 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 − 1 . 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.