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An intramolecular induction correction model of the molecular dipole moment.
Holt, Asbjørn; Karlström, Gunnar.
Afiliación
  • Holt A; Theoretical Chemistry, Chemical Center, Lund University, P.O.B 124, S-221 00 Lund, Sweden. asbjorn.holt@teokem.lu.se
J Comput Chem ; 29(7): 1084-91, 2008 May.
Article en En | MEDLINE | ID: mdl-18069665
A model for intramolecular polarization is presented. It is used to describe the changes in the molecular charge distribution occurring as a response to changes of dihedral angles in the molecule. The model is based on a multicenter multipole distribution of the molecular charge distribution. The electric field from this charge distribution induce dipole moments in the same molecule. The model contains atom type parameters to describe the damping of the electric field. A total of four atom types are used. The parameters are fitted to a calibration set with various functional groups, and tested against a validation set. The error obtained for the calibration set is reduced by 92% and by 88% for the validation set, if compared to an accurate state-of-the-art force field. It is shown that rotating the non-polarizable multicenter multipole distribution for the equilibrium geometry gives too large dipole moments for dihedral angles deviating from the equilibrium geometry. This will lead to too large long-range attractions in simulations. This problem is overcome by using the dipole polarizability correction suggested here, which gives dipole moments very close to the Hartree-Fock dipole moments obtained from reference calculations.
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Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Simulación por Computador / Modelos Químicos Idioma: En Revista: J Comput Chem Asunto de la revista: QUIMICA Año: 2008 Tipo del documento: Article País de afiliación: Suecia Pais de publicación: Estados Unidos
Buscar en Google
Colección: 01-internacional Base de datos: MEDLINE Asunto principal: Simulación por Computador / Modelos Químicos Idioma: En Revista: J Comput Chem Asunto de la revista: QUIMICA Año: 2008 Tipo del documento: Article País de afiliación: Suecia Pais de publicación: Estados Unidos