title: Analysis of the basis set superposition error in molecular dynamics of hydrogen-bonded liquids: application to methanol.
abstract: An efficient protocol is presented to compensate for the basis set superposition error (BSSE) in DFT molecular dynamics (MD) simulations using localized Gaussian basis sets. We propose a classical correction term that can be added a posteriori to account for BSSE. It is tested to what extension this term will improve radial distribution functions (RDFs). The proposed term is pairwise between certain atoms in different molecules and was calibrated by fitting reference BSSE data points computed with the counterpoise method. It is verified that the proposed exponential decaying functional form of the model is valid. This work focuses on hydrogen-bonded liquids, i.e., methanol, and more specific on the intermolecular hydrogen bond, but in principle the method is generally applicable on any type of interaction where BSSE is significant. We evaluated the relative importance of the Grimme-dispersion versus BSSE and found that they are of the same order of magnitude, but with an opposite sign. Upon introduction of the correction, the relevant RDFs, obtained from MD, have amplitudes equal to experiment.
authors.affiliation: Center for Molecular Modeling, QCMM Alliance Ghent-Brussels, Ghent University, Technologiepark 903, B-9052 Zwijnaarde, Belgium.
authors.forename: Marc
authors.initials: M
authors.lastname: Van Houteghem
authors.forename: Toon
authors.initials: T
authors.lastname: Verstraelen
authors.forename: An
authors.initials: A
authors.lastname: Ghysels
authors.forename: Louis
authors.initials: L
authors.lastname: Vanduyfhuys
authors.forename: Michel
authors.initials: M
authors.lastname: Waroquier
authors.forename: Veronique
authors.initials: V
authors.lastname: Van Speybroeck
mesh_terms: D006860:Hydrogen Bonding; D000432:Methanol / Q000737:chemistry*; D056004:Molecular Dynamics Simulation
chemical_list: D000432:Methanol