Issue 18, 2014

Aqueous solvation of HgClOH. Stepwise DFT solvation and Born–Oppenheimer molecular dynamics studies of the HgClOH–(H2O)24 complex

Abstract

We address the aqueous solvation of HgClOH through a systematic study of stepwise hydration considering the HgClOH–(H2O)n structures with n = 1–24. After calibration of the DFT method, the electronic calculations have been carried out using the B3PW91 exchange–correlation functional. For n < 5 the main geometrical parameters and incremental binding energies are in agreement with counterpoise-corrected MP2/AVTZ static values and BO-MP2 dynamic averages. For n > 15 three direct water–Hg interactions appear during the hydration process and a pentacoordinated trigonal bipyramid apical pattern around Hg is found. 22 water molecules are needed to build the first solvation shell. Unlike microsolvated HgCl2, no stable equatorial trigonal bipyramid was found. Optimizations with the Polarizable Continuum Model lead to structures with extremely large Hg–O(water) distances because of a dominant solvation effect on the explicit water molecules; however, this overestimation diminishes for large values of n. A DFT Born–Oppenheimer molecular dynamics simulation at T = 700 K revealed the stability of the HgClOH–(H2O)24 complex with an average trigonal bipyramid Hg-coordination pattern, in accordance with the static cluster description. After thermalization is achieved, the exchange rate of the Hg-coordinated water molecules is estimated to be ca. 1011 s−1.

Graphical abstract: Aqueous solvation of HgClOH. Stepwise DFT solvation and Born–Oppenheimer molecular dynamics studies of the HgClOH–(H2O)24 complex

Supplementary files

Article information

Article type
Paper
Submitted
19 Dec 2013
Accepted
14 Mar 2014
First published
17 Mar 2014

Phys. Chem. Chem. Phys., 2014,16, 8455-8464

Author version available

Aqueous solvation of HgClOH. Stepwise DFT solvation and Born–Oppenheimer molecular dynamics studies of the HgClOH–(H2O)24 complex

J. I. Amaro-Estrada, L. Maron and A. Ramírez-Solís, Phys. Chem. Chem. Phys., 2014, 16, 8455 DOI: 10.1039/C3CP55339F

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