Long-range effects in optimizing the geometry of stereoregular polymers. I. Formalism

Résultats de recherche: Contribution à un journal/une revueArticle

Résumé

We develop an original methodology to calculate analytically the long-range (LR) Coulombic effects to be included in Hartree-Fock forces computed on stereoregular polymers. The technique presented, based on multiple Taylor series expansions, is completely general and can be easily extended to all orders of expansion and to geometrical derivatives of higher order. In the McMurchie Davidson or similar schemes, the LR terms are added directly to Hermite integrals and LR effects are naturally considered during the computation of the energy and its derivatives. Each type of derivative (nuclear-repulsion energy, overlap and kinetic energy integrals, electron-nuclear attraction and two-electron integrals) is examined to quantify the impact of LR corrections. It turns out that the lattice sums of the gradients evaluated on a model macromolecule converge much faster when including those corrections. In addition, the dependence of the energy with respect to the unit cell length is for the first time considered in full details.

langue originaleAnglais
Pages (de - à)5306-5323
Nombre de pages18
journalThe journal of chemical physics
Volume111
Numéro de publication12
Les DOIs
étatPublié - 22 sept. 1999

Empreinte digitale

Polymers
formalism
Derivatives
Geometry
polymers
geometry
Taylor series
Electrons
Macromolecules
Kinetic energy
energy
series expansion
macromolecules
attraction
electrons
kinetic energy
methodology
gradients
expansion
cells

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abstract = "We develop an original methodology to calculate analytically the long-range (LR) Coulombic effects to be included in Hartree-Fock forces computed on stereoregular polymers. The technique presented, based on multiple Taylor series expansions, is completely general and can be easily extended to all orders of expansion and to geometrical derivatives of higher order. In the McMurchie Davidson or similar schemes, the LR terms are added directly to Hermite integrals and LR effects are naturally considered during the computation of the energy and its derivatives. Each type of derivative (nuclear-repulsion energy, overlap and kinetic energy integrals, electron-nuclear attraction and two-electron integrals) is examined to quantify the impact of LR corrections. It turns out that the lattice sums of the gradients evaluated on a model macromolecule converge much faster when including those corrections. In addition, the dependence of the energy with respect to the unit cell length is for the first time considered in full details.",
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Long-range effects in optimizing the geometry of stereoregular polymers. I. Formalism. / Jacquemin, Denis; André, Jean-Marie; Champagne, Benoit.

Dans: The journal of chemical physics, Vol 111, Numéro 12, 22.09.1999, p. 5306-5323.

Résultats de recherche: Contribution à un journal/une revueArticle

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