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We investigate the properties of norm-conserving pseudopotentials (effective core potentials) generated by inversion of the Hartree–Fock equations. In particular, we investigate the asymptotic be...
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Variational optimization of effective atom centered potentials for molecular properties

J. Chem. Phys. 122, 014113 (2005); doi:10.1063/1.1829051

Published 14 December 2004

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O. Anatole von Lilienfeld, Ivano Tavernelli, and Ursula Rothlisberger
Ecole Polytechnique Fédérale de Lausanne, Institut des Sciences et Ingénierie Chimiques, EPFL-BCH, CH-1015 Lausanne, Switzerland

Daniel Sebastiani
Max-Planck-Institut für Polymerforschung, Ackermannweg 10, D-55128 Mainz, Germany
In plane wave based electronic structure calculations the interaction of core and valence electrons is usually represented by atomic effective core potentials. They are constructed in such a way that the shape of the atomic valence orbitals outside a certain core radius is reproduced correctly with respect to the corresponding all-electron calculations. Here we present a method which, in conjunction with density functional perturbation theory, allows to optimize effective core potentials in order to reproduce ground-state molecular properties from arbitrarily accurate reference calculations within standard density functional calculations. We demonstrate the wide range of possible applications in theoretical chemistry of such optimized effective core potentials (OECPs) by means of two examples. We first use OECPs to tackle the link atom problem in quantum mechanics/molecular mechanics (QM/MM) schemes proposing a fully automatized procedure for the design of link OECPs, which are designed in such a way that they minimally perturb the electronic structure in the QM region. In the second application, we use OECPs in two sample molecules (water and acetic acid) such as to reproduce electronic densities and derived molecular properties of hybrid (B3LYP) quality within general gradient approximated (BLYP) density functional calculations. ©2005 American Institute of Physics.
History: Received 2 August 2004; accepted 14 October 2004; published 14 December 2004
Permalink: http://link.aip.org/link/?JCPSA6/122/014113/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.10.+z
    Theory of electronic structure, electronic transitions, and chemical binding in atoms and molecules
  • 34.20.-b
    Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions
  • 31.15.Ew
    Density-functional theory (atoms and molecules)
  • 31.15.Md
    Perturbation theory (atoms and molecules)
  • 02.60.Pn
    Numerical optimization
  • 31.15.Pf
    Variational techniques (atoms and molecules)
  • YEAR: 2005

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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