TY  - JOUR
U1  - Zeitschriftenartikel, wissenschaftlich - nicht begutachtet (unreviewed)
A1  - Kirschner, Karl
A1  - Reith, Dirk
A1  - Heiden, Wolfgang
T1  - The Performance of Dunning, Jensen and Karlsruhe Basis Sets on Computing Relative Energies and Geometries
T2  - ChemRxiv
N2  - 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.
UN  - https://nbn-resolving.org/urn:nbn:de:hbz:1044-opus-46977
SN  - 2573-2293
SS  - 2573-2293
U6  - https://doi.org/10.26434/chemrxiv.10303703
DO  - https://doi.org/10.26434/chemrxiv.10303703
SP  - 1
EP  - 24
PB  - American Chemical Society ACS
ER  -