skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Importance of charge transfer and polarization effects for the modeling of uranyl-cation complexes

Abstract

The structures, energies, and charges of uranyl cation complexes with water molecules, nitrate ion, and carbonate ions were determined using Hartree-Fock, second-order Moeller-Plesset (MP2) perturbation theory, and density functional theory (DFT) ab initio quantum chemical methods. Reasonable agreement with experimentally determined structures was found. Significant polarization of the ligands as well as charge transfer to the uranyl ion was observed in the complexes. The dissociation energy curves for the complexes were also determined at the MP2 level of theory. Attempts to reproduce these curves with molecular mechanical models with fixed atomic point charges failed, showing that an appropriate force field for these systems must include polarization and charge-transfer effects.

Authors:
; ; ;
Publication Date:
Research Org.:
Royal Veterinary and Agricultural Univ., Fredericksburg C (DK)
OSTI Identifier:
20034425
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 104; Journal Issue: 17; Other Information: PBD: 4 May 2000; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANYL COMPLEXES; HARTREE-FOCK METHOD; WATER; NITRATES; CARBONATES; POLARIZATION; ELECTRON TRANSFER; DISSOCIATION

Citation Formats

Hemmingsen, L., Amara, P., Ansoborlo, E., and Field, M.J. Importance of charge transfer and polarization effects for the modeling of uranyl-cation complexes. United States: N. p., 2000. Web. doi:10.1021/jp994395o.
Hemmingsen, L., Amara, P., Ansoborlo, E., & Field, M.J. Importance of charge transfer and polarization effects for the modeling of uranyl-cation complexes. United States. doi:10.1021/jp994395o.
Hemmingsen, L., Amara, P., Ansoborlo, E., and Field, M.J. Thu . "Importance of charge transfer and polarization effects for the modeling of uranyl-cation complexes". United States. doi:10.1021/jp994395o.
@article{osti_20034425,
title = {Importance of charge transfer and polarization effects for the modeling of uranyl-cation complexes},
author = {Hemmingsen, L. and Amara, P. and Ansoborlo, E. and Field, M.J.},
abstractNote = {The structures, energies, and charges of uranyl cation complexes with water molecules, nitrate ion, and carbonate ions were determined using Hartree-Fock, second-order Moeller-Plesset (MP2) perturbation theory, and density functional theory (DFT) ab initio quantum chemical methods. Reasonable agreement with experimentally determined structures was found. Significant polarization of the ligands as well as charge transfer to the uranyl ion was observed in the complexes. The dissociation energy curves for the complexes were also determined at the MP2 level of theory. Attempts to reproduce these curves with molecular mechanical models with fixed atomic point charges failed, showing that an appropriate force field for these systems must include polarization and charge-transfer effects.},
doi = {10.1021/jp994395o},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
issn = {1089-5639},
number = 17,
volume = 104,
place = {United States},
year = {2000},
month = {5}
}