Adsorption and dissociation of gas-phase HCl molecules on Al17q (q = −2 − +3) ions
- 12 Downloads
Al17 clusters exhibit apparent changes in curvature, which resemble macroscopic metal tips. Here, we show, using the density functional theory method, how surface charges of Al17q (q = −2 to +3) ions affect the adsorption and dissociation behavior of HCl molecules. Geometries, adsorption energies, vibrational frequencies, Mulliken population analysis and transition states of (Al17HCl)q (q = −2 to +3) adsorption complexes were studied. The results revealed that HCl molecules tend to locate on tip sites of the Al17q (q = −2 to +3) ions. Anionic adsorption complexes are prone to H affinity adsorption, whereas cationic adsorption complexes favor Cl-affinity adsorptions. These adsorption behaviors look quite like macroscopic tip effects. H–Cl bonds of the adsorption complexes weaken with an increase in either positive or negative charge. Dissociation barriers of the H–Cl bonds exhibit binding energies that are 2 orders of magnitude smaller than those of an isolated HCl molecule. Considering adsorption energies and dissociation barriers comprehensively, HCl molecules should dissociate spontaneously for all the models considered. Generally, the more negative charges the clusters carry, the more energy the reaction will release.
Keywords(Al17HCl)q (q = −2 − +3) ions Geometric structure Dissociation barrier Density functional theory
We are grateful to the reviewers for their valuable suggestions on improving our paper. The authors acknowledge grant from the Fundamental Research Fund for the Central Universities, Southwest University for Nationalities, China under Grant number 2017NZYQN44.
- 9.Liu T, Fu B, Zhang DH (2017) HCl dissociating on a rigid Au ( 111 ) surface : a six-dimensional quantum mechanical study on a new potential energy surface based on the RPBE functional HCl dissociating on a rigid Au ( 111 ) surface : a six-dimensional quantum mechanical study on a new. J Chem Phys 146:164706. https://doi.org/10.1063/1.4982051 CrossRefPubMedGoogle Scholar
- 13.Burgert R, Schnöckel H, Olzmann M, Bowen KH (2006) The chlorination of the [Al13]− cluster and the stepwise formation of its intermediate products, [Al11]−, [Al9]−, and [Al7]−: a model reaction for the oxidation of metals? Angew Chem Int Ed 45:1476–1479. https://doi.org/10.1002/anie.200502957 CrossRefGoogle Scholar
- 37.Herzberg G (1950) Molecular spectra and molecular structure I - spectra of diatomic molecules, 2nd edn. Van Nostrand Reinhold, New YorkGoogle Scholar
- 39.Lide DR (2003) Handbook of chemistry and physics on CD-ROM. CRC, Boca RatonGoogle Scholar