Issue 37, 2011
From the journal:

Physical Chemistry Chemical Physics

Theoretical study of the solvation of HgCl2, HgClOH, Hg(OH)2 and HgCl3−: a density functional theory cluster approach†

Ludovic Castro,a   Aurélien Dommergue,b   Alexandre Renard,b   Christophe Ferrari,b   Alejandro Ramirez-Solisc  and  Laurent Maron*a  

* Corresponding authors

a Université de Toulouse, INSA, UPS, LPCNO, 135 Avenue de Rangueil, F-31077 Toulouse, France
E-mail: laurent.maron@irsamc.ups-tlse.fr

b Laboratoire de Glaciologie et Géophysique de l'Environnement, CNRS/Université Joseph Fourier Grenoble I, 54 rue Molière, 38402 Saint Martin d'Hères, France

c Depto. de Física, Facultad de Ciencias, Universidad Autónoma del Estado de Morelos Cuernavaca, Morelos 62290, Mexico

Abstract

The determination of the solvation shell of Hg(II)-containing molecules and especially the interaction between Hg(II) and water molecules is the first requirement to understand the transmembrane passage of Hg into the cell. We report a systematic DFT study by stepwise solvation of HgCl2 including up to 24 water molecules. In order to include pH and salinity effects, the solvation patterns of HgClOH, Hg(OH)2 and HgCl3− were also studied using 24 water molecules. In all cases the hydrogen bond network is crucial to allow orbital-driven interactions between Hg(II) and the water molecules. DFT Born–Oppenheimer molecular dynamics simulations starting from the stable HgCl2–(H2O)24 structure revealed that an HgCl2–(H2O)3 trigonal bipyramid effective solute appears and then the remaining 21 water molecules build a complete first solvation shell, in the form of a water-clathrate. In the HgCl2, HgClOH, Hg(OH)2–(H2O)24 optimized structures Hg also directly interacts with 3 water molecules from an orbital point of view (three Hg–O donor–acceptor type bonds). All the other interactions are through hydrogen bonding. The cluster-derived solvation energies of HgCl2, HgClOH and Hg(OH)2 are estimated to be −34.4, −40.1 and −47.2 kcal mol−1, respectively.

Graphical abstract: Theoretical study of the solvation of HgCl2, HgClOH, Hg(OH)2 and HgCl3−: a density functional theory cluster approach

About
Cited by
Related
Download options Please wait...

Supplementary files

Article information

DOI
https://doi.org/10.1039/C1CP22154J
Article type
Paper
Submitted
01 Jul 2011
Accepted
03 Aug 2011
First published
22 Aug 2011

Phys. Chem. Chem. Phys., 2011,13, 16772-16779

Permissions

Request permissions

Theoretical study of the solvation of HgCl2, HgClOH, Hg(OH)2 and HgCl3−: a density functional theory cluster approach

L. Castro, A. Dommergue, A. Renard, C. Ferrari, A. Ramirez-Solis and L. Maron, Phys. Chem. Chem. Phys., 2011, 13, 16772 DOI: 10.1039/C1CP22154J

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements