Intermolecular interactions using small basis sets: Perturbation theory calculations avoiding basis set superposition error

In this work, the interaction of C 20 with N 2 X 2 ( X = H , F , Cl , Br , Me ) molecules has been explored using the B3LYP, M062x methods and 6-311G(d,p) and 6-311+G(d,p) basis sets. The interaction energies (IEs) obtained with standard method were corrected by basis set superposition error (BSSE) during the geometry optimization for all molecules at the same levels of theory. It was found C 20… N 2 H 2 interaction is stronger than the interaction of other N 2 X 2 ( X = F , Cl , Br , Me ) with C 20. Highest occupied and lowest unoccupied molecular orbitals (HOMO and LUMO, respectively) levels are illustrated by density of states spectra (DOS). The nucleus-independent chemical shifts (NICSs) confirm that C 20… N 2 X 2 molecules exhibit aromatic characteristics. Geometries obtained from DFT calculations were used to perform NBO analysis. Also, 14 N NQR parameters of the C 20… N 2 X 2 molecules are predicted.

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Double-Hybrid DFT Functionals for the Condensed Phase: Gaussian and Plane Waves Implementation and Evaluation

Molecules ◽

10.3390/molecules25215174 ◽

2020 ◽

Vol 25 (21) ◽

pp. 5174

Author(s):

Frederick Stein ◽

Jürg Hutter ◽

Vladimir V. Rybkin

Keyword(s):

Condensed Phase ◽

Density Functional ◽

Plane Waves ◽

Basis Set ◽

Basis Sets ◽

Density Functionals ◽

Basis Set Superposition Error ◽

Super Cell ◽

Long Range Interactions ◽

Function Correlation

Intermolecular interactions play an important role for the understanding of catalysis, biochemistry and pharmacy. Double-hybrid density functionals (DHDFs) combine the proper treatment of short-range interactions of common density functionals with the correct description of long-range interactions of wave-function correlation methods. Up to now, there are only a few benchmark studies available examining the performance of DHDFs in condensed phase. We studied the performance of a small but diverse selection of DHDFs implemented within Gaussian and plane waves formalism on cohesive energies of four representative dispersion interaction dominated crystal structures. We found that the PWRB95 and ωB97X-2 functionals provide an excellent description of long-ranged interactions in solids. In addition, we identified numerical issues due to the extreme grid dependence of the underlying density functional for PWRB95. The basis set superposition error (BSSE) and convergence with respect to the super cell size are discussed for two different large basis sets.

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Second-order energy components in basis-set-superposition-error-free intermolecular perturbation theory

Theoretical Chemistry Accounts ◽

10.1007/s00214-001-0299-5 ◽

2001 ◽

Vol 107 (1) ◽

pp. 38-47 ◽

Cited By ~ 6

Author(s):

A. Hamza ◽

Á. Vibók ◽

G. J. Halász ◽

I. Mayer

Keyword(s):

Perturbation Theory ◽

Second Order ◽

Basis Set ◽

Basis Set Superposition Error ◽

Order Energy ◽

Intermolecular Perturbation Theory ◽

Energy Components

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Intermolecular Effects on Third Order Nonlinear Optical Properties

MRS Proceedings ◽

10.1557/proc-247-93 ◽

1992 ◽

Vol 247 ◽

Cited By ~ 2

Author(s):

D. S. Dudis ◽

A. T. Yeates ◽

H. A. Kurtz

Keyword(s):

Optical Properties ◽

Intermolecular Interactions ◽

Nonlinear Optical ◽

Basis Set ◽

Basis Sets ◽

Intermolecular Potential ◽

Correlation Effects ◽

Third Order ◽

Hartree Fock ◽

Intermolecular Contacts

ABSTRACTHartree-Fock ab initio calculations have been used to examine the magnitude of non-polar intermolecular interactions on polarizabilities and second hyperpolarizabilities. In the present case two ethylene molecules were examined in a cofacial interaction. Basis set requirements and correlation effects were considered in deriving the intermolecular potential. Two basis sets were considered for the intermolecular interactions at the Hartree-Fock level, while one set of calculations was performed with corrections for correlation. It is found that intermolecular contacts at the van der Waals distance has little effect on the molecular second hyperpolarizability, but it is not clear what the effect would be for longer oligomers.

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Determination of the basis set superposition error with “DZP” basis sets in SCF calculations: CO + H2, NH3 + H2, H2 + H2

Chemical Physics ◽

10.1016/0301-0104(85)85023-0 ◽

1985 ◽

Vol 92 (2-3) ◽

pp. 287-294 ◽

Cited By ~ 21

Author(s):

L. Kurdi ◽

E. Kochansk ◽

G.H.F. Diercksen

Keyword(s):

Basis Set ◽

Basis Sets ◽

Basis Set Superposition Error ◽

Scf Calculations

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Halogen Interactions in Halogenated Oxindoles: Crystallographic and Computational Investigations of Intermolecular Interactions

Molecules ◽

10.3390/molecules26185487 ◽

2021 ◽

Vol 26 (18) ◽

pp. 5487

Author(s):

Rodrigo A. Lemos Silva ◽

Demetrio A. da Silva Filho ◽

Megan E. Moberg ◽

Ted M. Pappenfus ◽

Daron E. Janzen

Keyword(s):

Interaction Energy ◽

Intermolecular Interactions ◽

Density Functional ◽

Basis Set ◽

Interaction Energies ◽

Functional Theory ◽

Basis Set Superposition Error ◽

Reduced Density Gradient ◽

Moller Plesset ◽

Reduced Density

X-ray structural determinations and computational studies were used to investigate halogen interactions in two halogenated oxindoles. Comparative analyses of the interaction energy and the interaction properties were carried out for Br···Br, C-H···Br, C-H···O and N-H···O interactions. Employing Møller–Plesset second-order perturbation theory (MP2) and density functional theory (DFT), the basis set superposition error (BSSE) corrected interaction energy (Eint(BSSE)) was determined using a supramolecular approach. The Eint(BSSE) results were compared with interaction energies obtained by Quantum Theory of Atoms in Molecules (QTAIM)-based methods. Reduced Density Gradient (RDG), QTAIM and Natural bond orbital (NBO) calculations provided insight into possible pathways for the intermolecular interactions examined. Comparative analysis employing the electron density at the bond critical points (BCP) and molecular electrostatic potential (MEP) showed that the interaction energies and the relative orientations of the monomers in the dimers may in part be understood in light of charge redistribution in these two compounds.

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Accurate evaluation of SCF and MP2 components of interaction energies. Complexes of HF, OH2, and NH3 with Li+

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19882214 ◽

1988 ◽

Vol 53 (10) ◽

pp. 2214-2229 ◽

Cited By ~ 27

Author(s):

Małgorzata M. Szczęśniak ◽

Steve Scheiner

Keyword(s):

Point Charge ◽

Basis Set ◽

Basis Sets ◽

Interaction Energies ◽

Multipole Moments ◽

Gaussian Basis Sets ◽

Basis Set Superposition Error ◽

Polarization Functions ◽

Selection Of ◽

Correlation Corrections

High-quality Gaussian basis sets of the well-tempered type, containing three sets of polarization functions on all atoms, are used to investigate the interaction of Li+ with HF, OH2, and NH3. These sets reproduce the SCF and MP2 energies of the various monomers very well and, moreover, accurately treat the multipole moments and polarizabilities of the monomers. When applied to the complexes, the sets are essentially free of primary and secondary basis set superposition error at the SCF level; MP2 extension effects are also completely negligible while basis set superposition effects are small but non-negligible. Analysis of the correlation corrections to the molecular properties, coupled with comparison of the interaction of the bases with a point charge, provides a straightforward explanation of correlation contributions to the interaction energy. Recommendations are provided to guide selection of basis sets for molecular interactions so as to avoid distortion of the various components.

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