Accuracy of the electrostatic theorem for high‐quality Slater and Gaussian basis sets

Rico, J. Fernández; López, Rafael; Ema, I.; Ramı́rez, G.

doi:10.1002/qua.20088

Cited by 7 publications

(1 citation statement)

References 24 publications

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“…These reasons no longer hold. As it has been recently proved, densities computed with good Slater basis sets, and with very high quality Gaussian basis sets too, fulfill the electrostatic theorem with an accuracy that is sufficient for most quantitative applications and, a fortiori, for the qualitative ones as well. Moreover, a representation of the density 29-31 aimed to retain the identity of the atoms in a molecule as much as possible has also been reported, and that, in turn, facilitates the application of the electrostatic theorem.…”

Section: Introductionmentioning

confidence: 84%

Chemical Notions from the Electron Density

Rico

López

Ema

et al. 2005

J. Chem. Theory Comput.

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The study of density and the role played by its atomic representation is proposed as a way for the rationalization of chemical behavior. As this behavior has been long rationalized in terms of the basic concepts of empirical structural chemistry, a direct link between both approaches is searched for by using the exact representation of the density provided by the deformed atoms in molecules method (Rico, J. F.; López, R.; Ema, I.; Ramírez, G.; Ludeña, E. J. Comput. Chem. 2004, 25, 1355-1363). Noting that the spherical terms of the pseudoatoms cannot be mainly responsible for the chemical behavior, we study the small nonspherical deformations and find that they reflect and support all basic concepts of empirical structural chemistry. Lone pairs; single, double, and triple bonds; different classes of atoms; functional groups; and so forth are paralleled by the density deformations in a neat manner. These facts are illustrated with several examples.

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Section: Introductionmentioning

confidence: 84%

Chemical Notions from the Electron Density

Rico

López

Ema

et al. 2005

J. Chem. Theory Comput.

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Generation of basis sets with high degree of fulfillment of the Hellmann‐Feynman theorem

et al. 2007

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A direct relationship is established between the degree of fulfillment of the Hellman-Feynman (electrostatic) theorem, measured as the difference between energy derivatives and electrostatic forces, and the stability of the basis set, measured from the indices that characterize the distance of the space generated by the basis functions to the space of their derivatives with respect to the nuclear coordinates. On the basis of this relationship, a criterion for obtaining basis sets of moderate size with a high degree of fulfillment of the theorem is proposed. As an illustrative application, previously reported Slater basis sets are extended by using this criterion. The resulting augmented basis sets are tested on several molecules finding that the differences between energy gradient and electrostatic forces are reduced by at least one order of magnitude.

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