A possible definition of basis set superposition error

Davidson, Ernest R.; Chakravorty, Subhas J.

doi:10.1016/0009-2614(93)e1356-l

Cited by 131 publications

(46 citation statements)

References 127 publications

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“…The calculated dissociation energies are essentially the same for the 6-31G * and 6-31G * * basis sets; however, they decrease by roughly 1 kcal/mol in proceeding to the 6-31+G * * and again in going to the 6-311+G * * . This may reflect the diminishing effect of basis set superposition [47,48] (to be discussed further below). Since the B3PW91 results are closest to the experimental, this functional combination will be used (in conjunction with all four basis sets) for the dimer studies.…”

Section: Bond Lengths (å)mentioning

confidence: 99%

“…This is accompanied by increases in the separations between the two monomer units. All of these changes can perhaps be attributed to a lessening of the consequences of basis set superposition; this refers to the spurious stabilization of a system relative to its fragments because the basis functions of the latter augment each other in describing the former [47,48]. A "counterpoise" technique was proposed as a correction for this problem [48,57,58], but there has been a great deal of disagreement concerning its effectiveness, and it has been shown to sometimes actually worsen the accuracy of the results.…”

Section: Dimers Of Dimethylnitraminementioning

confidence: 99%

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Density functional study of dimers of dimethylnitramine

Politzer

Concha

Murray

2000

Int. J. Quantum Chem.

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Section: Bond Lengths (å)mentioning

confidence: 99%

Section: Dimers Of Dimethylnitraminementioning

confidence: 99%

Density functional study of dimers of dimethylnitramine

Politzer

Concha

Murray

2000

Int. J. Quantum Chem.

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“…Before proceeding to the energetic analysis of the FeÀ ÀCO and FeÀ ÀCN bond in the complexes studied, we have investigated the effect of basis set incompleteness by calculating the basis set superposition error (BSSE) on DE int energies via the counterpoise method [38][39][40][41] for the all carbonyl complexes of Fe 0 (1a) and Fe 21 (7b). In the case of the trigonal bipyramidal complex, 1a, the BSSE has been calculated equal to 0.9 kcal/mol for both the Fe(CO) 5 À ÀCO ax and the Fe(CO) 5 À ÀCO eq bonds compared with interaction energies of 53.1 kcal/mol and 49.1 kcal/ mol respectively.…”

Section: Bonding Analysismentioning

confidence: 99%

Density functional investigation and bonding analysis of pentacoordinated iron complexes with mixed cyano and carbonyl ligands

Tsalavoutis¹,

Sigalas²

2010

J Comput Chem

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The equilibrium structures and vibrational frequencies of the iron complexes [Fe(0)(CN)(n)(CO)(5-n)](n-) and [Fe(II)(CN)(n)(CO)(5-n)](2-n) (n = 0-5) have been calculated at the BP86 level of theory. The Fe(0) complexes adopt trigonal bipyramidal structures with the cyano ligands occupying the axial positions, whereas corresponding Fe(2+) complexes adopt square pyramidal structures with the cyano ligands in the equatorial positions. The calculated geometries and vibrational frequencies of the mixed iron Fe(0) carbonyl cyanide complexes are in a very good agreement with the available experimental data. The nature of the Fe-CN and Fe-CO bonds has been analyzed with both charge decomposition and energy partitioning analysis. The results of energy partitioning analysis of the Fe-CO bonds shows that the binding interactions in Fe(0) complexes have 50-55% electrostatic and 45-50% covalent character, whereas in Fe(2+) 45-50% electrostatic and 50-55% covalent character. There is a significant contribution of the pi- orbital interaction to the Fe-CO covalent bonding which increases as the number of the cyano groups increases, and the complexes become more negatively charged. This contribution decreases in going from Fe(0) to Fe(2+) complexes. Also, this contribution correlates very well with the C-O stretching frequencies. The Fe-CN bonds have much less pi-character (12-30%) than the Fe-CO bonds.

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“…This refers to the size-imbalance between the basis sets used for M and the M i , which are smaller. The result is an artificial stabilization of M [1][2][3]. The effect diminishes with the use of larger basis sets, but this solution again involves increased computational cost.…”

Section: Introductionmentioning

confidence: 99%

“…We used the methodology that has been outlined to determine E es for several molecular dimers [15] 2 . This was done primarily at several Hartree-Fock levels.…”

Section: Applicationsmentioning

confidence: 99%

Electronic Density Approaches to the Energetics of Noncovalent Interactions

Politzer

2004

IJMS

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Abstract:We present an overview of procedures that have been developed to compute several energetic quantities associated with noncovalent interactions. These formulations involve numerical integration over appropriate electronic densities. Our focus is upon the electrostatic interaction between two unperturbed molecules, the effect of the polarization of each charge distribution by the other, and the total energy of interaction. The expression for the latter is based upon the Hellmann-Feynman theorem. Applications to a number of systems are discussed; among them are dimers of uracil and interacting pairs of molecules in the crystal lattice of the energetic compound RDX.

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A possible definition of basis set superposition error

Cited by 131 publications

References 127 publications

Density functional study of dimers of dimethylnitramine

Density functional study of dimers of dimethylnitramine

Density functional investigation and bonding analysis of pentacoordinated iron complexes with mixed cyano and carbonyl ligands

Electronic Density Approaches to the Energetics of Noncovalent Interactions

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