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Analysis of the basis set superposition error in molecular dynamics of hydrogen-bonded liquids : application to methanol
- Source :
- JOURNAL OF CHEMICAL PHYSICS, The Journal of Chemical Physics
- Publication Year :
- 2012
-
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.
- Subjects :
- 1ST PRINCIPLES SIMULATIONS
Gaussian
VIBRATIONAL FREQUENCIES
General Physics and Astronomy
Molecular Dynamics Simulation
010402 general chemistry
01 natural sciences
DENSITY-FUNCTIONAL THEORY
INTERMOLECULAR INTERACTIONS
Molecular dynamics
symbols.namesake
FREE SCF ALGORITHM
Quantum mechanics
0103 physical sciences
STRUCTURE REFINEMENT
Statistical physics
Physical and Theoretical Chemistry
AB-INITIO
010304 chemical physics
Basis (linear algebra)
Chemistry
Methanol
Intermolecular force
SOLVENT ELECTROSTATIC POTENTIALS
Hydrogen Bonding
GENERALIZED GRADIENT APPROXIMATION
0104 chemical sciences
Exponential function
NEUTRON-DIFFRACTION
Physics and Astronomy
symbols
Density functional theory
Counterpoise
Order of magnitude
Subjects
Details
- Language :
- English
- ISSN :
- 00219606
- Database :
- OpenAIRE
- Journal :
- JOURNAL OF CHEMICAL PHYSICS, The Journal of Chemical Physics
- Accession number :
- edsair.doi.dedup.....b2edc80ffd72523732f9eb9dbf0cb9d8