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Density functional study on electronic structure, nature of bonding and reactivity of NO adsorbed Rhn0/± (n=2-8) clusters

Abstract

Systematic investigation on lowest energy NO adsorbed neutral and ionic Rhn (n=2-8) clusters in the gas phase are executed with all electron relativistic method using density functional theory (DFT) within the generalized gradient approximation. Geometrical parameters like bond length, adsorption energy, vibrational stretching frequency and reactivity parameters such as electron density, density of states (DOS), LUMO (Lowest unoccupied molecular orbital), HOMO (Highest occupied molecular orbital) etc are evaluated to understand the bonding nature as well as the binding interaction of NO with stable Rhn0/± (n=2-8) clusters. RhnNO- clusters are found to be more stable on the basis of adsorption energy in comparison to RhnNO0/+. Synergic bond formation is noticed between rhodium atom and NO molecule due to back-donation of electron from metal d- orbitals to π* orbital of NO in the case of RhnNO0/-. Deformed electron density also suggests stronger bond between rhodium and N atom of NO molecule in RhnNO-. HOMO and LUMO isosurface diagrams reveal that electrons are delocalized from d-orbitals of rhodium (HOMO) to π* orbital of NO (LUMO). Mülliken charge analysis along with electron density distribution also show the higher stability of RhnNO- clusters in comparison to RhnNO0/+. Energy profile diagrams for the conversion of NO to NO2 catalysed by neutral and ionic Rhn clusters reveal the lower activation barrier for anionic Rhn in comparison to Rhn0/+ except Rh7. Anionic Rh4 and Rh6 clusters are seen to be catalytically more active for the conversion of NO to NO2.

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Publication details

The article was received on 27 Oct 2017, accepted on 05 Dec 2017 and first published on 06 Dec 2017


Article type: Paper
DOI: 10.1039/C7NJ04166G
Citation: New J. Chem., 2017, Accepted Manuscript
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    Density functional study on electronic structure, nature of bonding and reactivity of NO adsorbed Rhn0/± (n=2-8) clusters

    P. Mondal and A. Dutta, New J. Chem., 2017, Accepted Manuscript , DOI: 10.1039/C7NJ04166G

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