Possible generalizations of the Boys-Bernardi counterpoise correction scheme to the case of relaxed monomer geometries is discussed. It is emphasized that the monomer relaxation energy should be calculated in the basis of free monomers, because it becomes ambiguous in the supermolecule basis.
Bond functions, covalent potential curves, and the basis set superposition error
β Scribed by James S. Wright; V. J. Barclay
- Publisher
- John Wiley and Sons
- Year
- 1991
- Tongue
- English
- Weight
- 803 KB
- Volume
- 12
- Category
- Article
- ISSN
- 0192-8651
No coin nor oath required. For personal study only.
β¦ Synopsis
In the current practice of quantum chemistry, it is not clear whether corrections for basis set superposition errors should be applied to the calculation of potential energy curves, in order to improve agreement with experimental data. To examine this question, spectroscopic parameters derived from theoretical potential curves are reported for the homonuclear diatomics C,, N,, O,, and F,, using a configuration interaction method. Three different basis sets were used, including double zeta plus polarization, triple zeta plus double polarization, and double zeta polarization augmented by bond functions. The bond function basis sets, which were optimized in the preceding paper to obtain accurate dissociation energies, also gave the most accurate parameters. The potential curves were then corrected for basis set superposition error using the counterpoise correction, and the spectroscopic parameters were computed again. The BSSE-corrected curves showed worse agreement with experiment for all properties than the original (uncorrected) curves. The reasons for this finding are discussed. In addition to the numerical results, some problems in the application of the BSSE correction to basis sets containing bond functions are shown. In particular, there is an overcounting of the lowering due to the bond functions, regardless of which type of correction is applied. Also, genuine BSSE affects cannot be separated from energy-lowering effects due to basis set incompleteness, and we postulate that it is the latter which is strongly dominant in the calculation of covalent potential curves. Based on these arguments, two conclusions follow: (1) application of BSSE corrections to potential curves should not be routinely applied in situations where the bonding is strong, and (2) appropriate use of bond functions can lead to systematic improvement in the quality of potential curves.
π SIMILAR VOLUMES
## Abstract The effect of the addition of diffuse functions of __sp__ type on the first row atoms (and/or of __d__ type on phosphorus) to a MINIβ1 minimal basis set is evaluated by comparing the SCF description of the interaction energy and its decomposition, counterpoise (CP) corrected and uncorre
The validrty of the criterion used by Collins and Gallup to establish whether the counterpotse correction overestimates the basis set superpositton error 1s called mto question. Results supporting the original Boys and Bemardi function counterpoise method are presented.
## Abstract We evaluate the performance of ten functionals (B3LYP, M05, M05β2X, M06, M06β2X, B2PLYP, B2PLYPD, X3LYP, B97D, and MPWB1K) in combination with 16 basis sets ranging in complexity from 6β31G(d) to augβccβpV5Z for the calculation of the Hβbonded water dimer with the goal of defining which
The supermolecule interaction energies at the self-consistent field and the second-order Moller-Plesset perturbation theory levels are analyzed using the polarization approximation perturbation theory of intermolecular interactions. The results for the He-H+ complex show that the perturbation expans
Gutowski, van Duijneveldt, Chafasinski, and Piela have criticized our analysis of the function counterpoise correction and our conclusion that the correction using the full basis for monomer calculations overcorrects for basis set superposition error. An analysis of their argument shows, however, th