Open AccessSmall Atomic Orbital Basis Set First‐Principles Quantum Chemical Methods for Large Molecular and Periodic Systems: A Critical Analysis of Error Sources
Author(s) -
Sure Rebecca,
Brandenburg Jan Gerit,
Grimme Stefan
Publication year - 2016
Publication title -
chemistryopen
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.644
H-Index - 29
ISSN - 2191-1363
DOI - 10.1002/open.201500192
Subject(s) - basis set , basis (linear algebra) , statistical physics , computation , superposition principle , quantum chemistry , density functional theory , set (abstract data type) , quantum , computational chemistry , molecular orbital , supramolecular chemistry , quantum mechanics , theoretical physics , computer science , physics , chemistry , mathematics , algorithm , molecule , geometry , programming language
Abstract In quantum chemical computations the combination of Hartree–Fock or a density functional theory (DFT) approximation with relatively small atomic orbital basis sets of double‐zeta quality is still widely used, for example, in the popular B3LYP/6‐31G* approach. In this Review, we critically analyze the two main sources of error in such computations, that is, the basis set superposition error on the one hand and the missing London dispersion interactions on the other. We review various strategies to correct those errors and present exemplary calculations on mainly noncovalently bound systems of widely varying size. Energies and geometries of small dimers, large supramolecular complexes, and molecular crystals are covered. We conclude that it is not justified to rely on fortunate error compensation, as the main inconsistencies can be cured by modern correction schemes which clearly outperform the plain mean‐field methods.