Efficiency of numerical basis sets for predicting the binding energies of hydrogen bonded complexes: Evidence of small basis set superposition error compared to Gaussian basis sets

2007 ◽  
Vol 29 (2) ◽  
pp. 225-232 ◽  
Author(s):  
Yasuji Inada ◽  
Hideo Orita
Keyword(s):  
Binding Energies ◽  
Basis Set ◽  
Basis Sets ◽  
Gaussian Basis Sets ◽  
Basis Set Superposition Error ◽  
Bonded Complexes ◽  
Hydrogen Bonded

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

1988 ◽  
Vol 53 (10) ◽  
pp. 2214-2229 ◽  
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.

STACKING INTERACTION IN PYRAZINE DIMER

2006 ◽  
Vol 05 (03) ◽  
pp. 609-619 ◽  
Author(s):  
BRIJESH KUMAR MISHRA ◽  
N. SATHYAMURTHY
Keyword(s):  
Center Of Mass ◽  
Binding Energies ◽  
Mass Separation ◽  
Basis Set ◽  
Basis Sets ◽  
Mutual Orientation ◽  
Coupled Cluster ◽  
Basis Set Superposition Error ◽  
Moller Plesset ◽  
Plesset Perturbation Theory

The structure and stability of pyrazine dimer in different orientations have been investigated using second- and fourth-order Møller–Plesset perturbation theory (MP2, MP4) and coupled-cluster singles and doubles with non-iterative perturbative triples method [CCSD(T)] with various basis sets (6-31G*, 6-311G**, 6-311++G**, cc-pVDZ, aug-cc-pVDZ, cc-pVTZ, and aug-cc-pVTZ). With the largest basis set (aug-cc-pVTZ) at the MP2 level of theory, the calculated binding energies (basis set superposition error corrected) for the sandwich, N–N axial-displaced, lateral-displaced, cross-displaced, T-shaped ( T N-ring and T H-ring ), and wedge-shaped ( W N–C and W C–C ) geometries are found to be 3.01, 4.18, 4.63, 5.92, 4.54, 2.78, 2.89, and 3.23 kcal/mol, respectively. Although MP2 calculations predict the cross-displaced geometry to be the most stable one, MP4 and CCSD(T) calculations show the most stable geometry to be T-shaped ( T N-ring ), with a center-of-mass separation of 4.2 Å. Dispersion interaction seems to be the major source of attraction in all the geometries considered, while the nature of electrostatic interaction depends on the mutual orientation of the two rings.

Counterpoise-Corrected Potential Energy Surfaces of Simple Hydrogen-Bonded Systems

1998 ◽  
Vol 63 (9) ◽  
pp. 1343-1354 ◽  
Author(s):  
Pavel Hobza ◽  
Zdeněk Havlas
Keyword(s):  
Potential Energy Surfaces ◽  
Correlation Energy ◽  
Linear Structure ◽  
Water Dimer ◽  
Basis Set ◽  
Basis Sets ◽  
Basis Set Superposition Error ◽  
Gradient Optimization ◽  
Intermolecular Distances ◽  
Hydrogen Bonded

Geometric and energetic characteristics of various simple hydrogen-bonded complexes (water dimer, hydrogen fluoride dimer, formamide dimer, formic acid dimer, glycine dimer) have been studied by gradient optimization, which a priori eliminates the basis set superposition error (BSSE) by using the counterpoise (CP) method, as well as by the standard gradient optimization. Calculations were done at the Hartree-Fock, correlated MP2 and DFT levels with small- and medium-basis sets. The CP-corrected and standard PESs differ, depending on the theoretical level used. Larger differences were found if the correlation energy was included. Intermolecular distances from the CP-corrected PES are consistently longer, and the respective difference may be significant (≈0.1 A). The stabilization energies obtained from the CP-corrected PES are always larger than those from the standard PES. Optimization at the standard PES might result in a wrong structure. For example, the "quasi-linear" structure of the (HF)2 (global minimum) does not exist at the standard MP2/6-31G** and DFT/B3LYP/6-31G** PESs and it is found only when passing to the respective CP-corrected PESs.

A DFT STUDY OF MOLYBDATE-PHOSPHONIC ACID COMPLEX

2009 ◽  
Vol 08 (04) ◽  
pp. 765-772 ◽  
Author(s):  
M. AGHAIE ◽  
M. H. GHORBANI ◽  
R. FAZAELI ◽  
H. AGHAIE
Keyword(s):  
Phosphonic Acid ◽  
Relative Stability ◽  
Density Functional ◽  
Binding Energies ◽  
Basis Set ◽  
Basis Sets ◽  
Equilibrium Geometry ◽  
Dft Methods ◽  
Acid Complex ◽  
Basis Set Superposition Error

The relative stability of Molybdate-Phosphonic Acid (MPA) Complex in gas phase has been carried out using Density Functional Theory (DFT) methods. The methods used for calculations are B3LYP, BP86 and B3PW91, with three series of basis sets: D95**, 6-31+G (d,p) and 6-31++G (d,p) for hydrogen and oxygen atoms; LANL2DZ for Mo and Phosphorus. Predicted geometry and relative stability are discussed. Equilibrium geometry in the ground electronic state energy has been calculated for 1:1 complex. The best result for energetic and geometrical ground state was obtained with Becke3LYP calculations. The Basis Set Superposition Error (BSSE) begins to converge for all methods/basis sets. For this complex, most levels of theory seem to give reasonable estimates of the known binding energies, but here, too, the BSSE overwhelms the reliability of the binding energies for these basis sets.

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