Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 7, Issue 1, Pages 138-147Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct1004005
Keywords
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Funding
- GENCI (CINES/IDRIS) [2009-075009, x2010075027]
- Centre de Ressources Informatiques de Haute Normandie (CRIHAN, Rouen, France) [1998053, 2008011]
- French National Research Agency (ANR) [2008CESA-020]
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Reduced Variational Space (RVS) calculations are reported that afford insight into the energetic origins of the hemi- and holo-directing behavior of [Pb(H2O)(n)](2+) complexes. It is shown that the distribution of ligands around the Pb2+ center arises from a delicate balance between the first-order Coulomb plus exchange-repulsion energy that favors holo-directionality, and the second-order charge transfer plus polarization term that favors hemi-directionality. It is additionally demonstrated that the pseudopotential/basis set combination used to study such complexes should be carefully selected, as artifacts can arise when using large-core pseudopotentials. Finally, based on these findings, we introduce a new SIBFA force field parametrization for Pb2+. Results yield close agreement with ab initio complexation energies in a series of [Pb(H2O)(n)](2+) complexes and successfully encapsulate the hemi- and holo-directing properties. SIBFA thus appears to be the first classical force field to be able to model the holo-/hemi-directed transition within Pb complexes, avoiding the need for explicit wave function treatment and consequently providing the opportunity to deal with large leaded systems of biological interest.
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