Stepwise basis set selection

Abstract

The computational cost of quantum chemical methods grows rapidly with increasing level of theory and basis set size. At increasing costs, higher accuracies can be reached, forcing a compromise between cost and accuracy for most molecular systems. Heats of reaction, however, are mostly determined by a subset of atoms that experience significant bonding and/or electronic changes. To exploit this fact, the Stepwise Basis Builder (SBB) algorithm selectively adds basis functions to reactive atoms and maintains small basis sets on spectator atoms. This article introduces the SBB algorithm and how it chooses a basis for each atom, predicts calculation errors, and uses these predicted errors to reach target levels of accuracy. Benchmarks show SBB heats of reaction and activation barriers converge to values consistent with higher-quality calculations using a greatly reduced number of basis functions. V C 2018 Wiley Periodicals, Inc.

Exploring borderline SN1–SN2 mechanisms: the role of explicit solvation protocols in the DFT investigation of isopropyl chloride

“…38 The choice of a double-zeta basis set over a quadruple-zeta one was driven by the computational cost associated with the simulated systems. 39 A brief discussion on the Basis Set Superposition Error (BSSE) and its correction 40,41 in describing our system is included in the ESI. † Additionally, the M06-2X/ aug-cc-pVDZ combination has been previously recommended for calculations involving H-bonded water dimers, 42 which plays a crucial role in our analyses of hydrolysis reactions.…”