Hydration Structure of Pb(II) from Density Functional Theory Studies and First-Principles Molecular Dynamics

An Ab Initio Investigation of the Hydration of Lead(II)

“…The results of Lei and Pan seem to suggest that the lowest energy structures of aqualead(II) complexes have tetracoordination, although with low-lying higher-coordination structures close in energy [20]. Molecular dynamics studies give varying numbers for the hydration number of lead (e.g., 8.1 [19], 6.3 [21], 4 [22]). Clearly the result has a strong dependence on the potential (level of theory) used, which is a main point we are trying to make.…”

“…Lead(II), like bismuth(III) [21] might be expected to show deviations from the ideal symmetry point groups listed above, due to the potentially stereochemically active inert 6s 2 subshell. The point group symmetry for the mono-through octaaquabismuth(III) was found to be C 2v , C 2 , C 3 , C 2 , C 2v , C 3 , C 2 , and S 8 , respectively.…”

“…They found stable conformations for n = 6-8, but not for 9, and the hemi-to holodirected transition occurred at n = 6. They found a hydration number of 6.3 [21]. Leon-Pimentel et al performed Born-Oppenheimer molecular dynamics (BOMD) simulations using the aug-cc-pVDZ-pp basis set and effective core potential on lead and both the 6-311G and aug-cc-pVDZ basis sets on oxygen and hydrogen.…”

Structure and bonding nature of [PbCl]+ adsorption on the kaolinite(0 0 1) surface in aqueous system

“…Comparing with the Pb O interaction, less antibonding contribution of Pb 6s Cl 3p than that of Pb 6s O 2p may act as the main reason for the large positive value of Pb Cl population. As the antibonding state filling is closely related to the stereochemical effect of n s 2 lone pair [37][38][39] and depends strongly on the cation-anion interaction [36,40], difference in the ligating atoms of Pb(II) determines the proportion of electron filling into the bonding and antibonding states. Ligand of chlorine features relatively large atomic radius and weak electronegativity, and can only coordinate with Pb(II) at a slightly father distance.…”