%0 Journal Article %T Theoretical study of the solvation of HgCl2, HgClOH, Hg(OH)2 and HgCl3−: a density functional theory cluster approach %+ Laboratoire de physique et chimie des nano-objets (LPCNO) %+ CHANG (CHANG) %+ Departamento de Fisica %A Castro, Ludovic %A Dommergue, A. %A Renard, A. %A Ferrari, C. %A Ramírez-Solís, A. %A Maron, Laurent %Z CALMIP, CINES, EC2CO %< avec comité de lecture %@ 1463-9076 %J Physical Chemistry Chemical Physics %I Royal Society of Chemistry %V 13 %N 37 %P 16772-16779 %8 2011-08-22 %D 2011 %R 10.1039/C1CP22154J %Z Sciences of the Universe [physics]/Earth Sciences/GlaciologyJournal articles %X 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. %G English %Z ECOS-ANUIES/CONACYT basic science project No. 130931 %L insu-00646729 %U https://insu.hal.science/insu-00646729 %~ INSU %~ UNIV-SAVOIE %~ UNIV-TLSE3 %~ UGA %~ CNRS %~ UNIV-GRENOBLE1 %~ INSA-TOULOUSE %~ INPG %~ IRSTEA %~ INC-CNRS %~ AGREENIUM %~ LPCNO %~ INSA-GROUPE %~ INRAE %~ USMB-COMUE %~ TOULOUSE-INP %~ UNIV-UT3 %~ UT3-INP %~ UT3-TOULOUSEINP %~ TEST2-HALCNRS