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

Literature Information

Publication Date 2006-08-22
DOI 10.1039/B608719A
Impact Factor 3.676
Authors

Andreas Markmann, Jacob L. Gavartin, Alexander L. Shluger


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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