The choice of basis sets for an investigation can be difficult, especially considering the different basis set families available and their various nomenclature. In an effort to assist researchers in this choice, we present an MP2 systematic study on the accuracy of computed relative energies and geometries. Five minima and fourteen 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. VnZ and AVnZ, n=2-5), twenty-five Jensen (i.e. pc-n, pcseg-n, aug-pcseg-n, pcSseg-n and aug-pcSseg-n, n=1-5) and nine Karlsruhe (e.g. def2-SV(P), def2-QZVPPD) basis sets. The molecules were chosen as representatives of closed-shell, neutral species that have a) electron delocalization with a very small dipole moment, b) an electronegative atom with a strong dipole, and c) a hydrogen bonded dimer. Using MP2/CBS relative energies as target values, fifteen basis sets are within 0.05 kcal/mol and an additional seven are within 0.1 kcal/mol of those values. A simple equation is also presented that ranks the basis sets through an adjustable factor that balances the relative importance of the calculational cost and accuracy. As an illustration, specifying a 40:60 (cost:accuracy) balance results in a ranking of AVTZ (1st), aug-pcseg-3 (2nd) and def2-QZVPP (3rd).

Performance of Dunning, Jensen, and Karlsruhe basis sets on computing relative energies and geometries of mimima and transitions states

2019 Fall National Meeting

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