Issue 37, 2006
From the journal:

Physical Chemistry Chemical Physics

Chemisorption of HCl to the MgO(001) surface: A DFT study†

Andreas Markmann,*a   Jacob L. Gavartinb  and  Alexander L. Shlugerb  

* Corresponding authors

a Theoretische Chemie, Technische Universität München, Lichtenbergstraße 4, Garching, Germany
E-mail: andreas.markmann@ch.tum.de

b Department of Physics and Astronomy and London Centre for Nanotechnology, University College London, Gower Street, London, UK

Abstract

We use plane wave and embedded cluster ab initio density functional calculations to study adsorption, dissociation and diffusion of the HCl molecule on the MgO(001) surface. The two methods yield comparable results for adsorption of an isolated HCl molecule and complement each other when considering charged species and coverage effects. We find dissociative chemisorption at a coverage smaller than 0.5 monolayer with a Cl− ion electrostatically coupled to the OH− ion at the surface oxygen site. The adsorption energy of the Cl−⋯(OH)− complex is 1.5 eV and the activation energy of Cl− diffusion away from OH− is 0.6 eV. There is no significant activation energy for rotation of Cl− around the adsorption site. At rising coverage, an increase in dipole–dipole repulsion between HCl molecules leads to a lowering of the adsorption energy per HCl and a change of binding towards hydrogen-bridge type as well as a lowering of the activation energy for Cl− diffusion. OH− formed in the surface due to HCl adsorption has a stretch frequency of 3083 cm−1 with Cl− associated and 3648 cm−1 with Cl− removed.

Graphical abstract: Chemisorption of HCl to the MgO(001) surface: A DFT study

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Article information

DOI
https://doi.org/10.1039/B608719A
Article type
Paper
Submitted
20 Jun 2006
Accepted
14 Aug 2006
First published
22 Aug 2006

Phys. Chem. Chem. Phys., 2006,8, 4359-4367

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Chemisorption of HCl to the MgO(001) surface: A DFT study

A. Markmann, J. L. Gavartin and A. L. Shluger, Phys. Chem. Chem. Phys., 2006, 8, 4359 DOI: 10.1039/B608719A

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