Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters

The experimental and theoretical adiabatic ionization energies IEs of the rhodium-holmium bimetallic clusters RhHo2On n=0-2 have been determined using photoionization efficiency spectroscopy and density functional theory DFT calculations. Both sets of data show the IE of RhHo2O to be significantly l...

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Main Authors: Gentleman, A., Addicoat, M., Dryza, V., Gascooke, J., Buntine, Mark, Metha, G.
Format: Journal Article
Published: American Institute of Physics 2009
Subjects:
Online Access:http://hdl.handle.net/20.500.11937/12479
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author Gentleman, A.
Addicoat, M.
Dryza, V.
Gascooke, J.
Buntine, Mark
Metha, G.
author_facet Gentleman, A.
Addicoat, M.
Dryza, V.
Gascooke, J.
Buntine, Mark
Metha, G.
author_sort Gentleman, A.
building Curtin Institutional Repository
collection Online Access
description The experimental and theoretical adiabatic ionization energies IEs of the rhodium-holmium bimetallic clusters RhHo2On n=0-2 have been determined using photoionization efficiency spectroscopy and density functional theory DFT calculations. Both sets of data show the IE of RhHo2O to be significantly lower than the values for RhHo2 and RhHo2O2, which are found to be similar. This indicates that there are significant changes in electronic properties upon sequential addition of oxygen atoms to RhHo2. The DFT investigations show that the lowest energy neutral structures are a C2v triangle for RhHo2, a C2v planar structure for RhHo2O where the O atom is doubly bridged to the Ho-Ho bond, and a C2v nonplanar structure for RhHo2O2, where the O2 is dissociative and each O atom is doubly bridged to the Ho-Ho bond in the cluster above and below the RhHo2 trimer plane. Good correlation between the experimental and computational IE data imply that the lowest energy neutral structures calculated are the most likely isomers ionized in the molecular beam. In particular, the theoretical adiabatic IE for the dissociative RhHo2O2 structure is found to compare better with the experimentally determined value than the corresponding lowest energy O2 associative structure.
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spelling curtin-20.500.11937-124792019-02-19T05:34:47Z Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters Gentleman, A. Addicoat, M. Dryza, V. Gascooke, J. Buntine, Mark Metha, G. Carbide Clusters Infrared-Spectra Dissociation-Energies Electronic-Structures Catalytic Co Oxidation Gas-Phase Reactions Lanthanide Metal-Clusters Structural-Characterization Ionization-Potentials Threshold Photoionization The experimental and theoretical adiabatic ionization energies IEs of the rhodium-holmium bimetallic clusters RhHo2On n=0-2 have been determined using photoionization efficiency spectroscopy and density functional theory DFT calculations. Both sets of data show the IE of RhHo2O to be significantly lower than the values for RhHo2 and RhHo2O2, which are found to be similar. This indicates that there are significant changes in electronic properties upon sequential addition of oxygen atoms to RhHo2. The DFT investigations show that the lowest energy neutral structures are a C2v triangle for RhHo2, a C2v planar structure for RhHo2O where the O atom is doubly bridged to the Ho-Ho bond, and a C2v nonplanar structure for RhHo2O2, where the O2 is dissociative and each O atom is doubly bridged to the Ho-Ho bond in the cluster above and below the RhHo2 trimer plane. Good correlation between the experimental and computational IE data imply that the lowest energy neutral structures calculated are the most likely isomers ionized in the molecular beam. In particular, the theoretical adiabatic IE for the dissociative RhHo2O2 structure is found to compare better with the experimentally determined value than the corresponding lowest energy O2 associative structure. 2009 Journal Article http://hdl.handle.net/20.500.11937/12479 10.1063/1.3120442 American Institute of Physics restricted
spellingShingle Carbide Clusters
Infrared-Spectra
Dissociation-Energies
Electronic-Structures
Catalytic Co Oxidation
Gas-Phase Reactions
Lanthanide Metal-Clusters
Structural-Characterization
Ionization-Potentials
Threshold Photoionization
Gentleman, A.
Addicoat, M.
Dryza, V.
Gascooke, J.
Buntine, Mark
Metha, G.
Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title_full Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title_fullStr Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title_full_unstemmed Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title_short Photoionization efficiency spectroscopy and density functional theory investigations of RhHo2On, (n=0-2) clusters
title_sort photoionization efficiency spectroscopy and density functional theory investigations of rhho2on, (n=0-2) clusters
topic Carbide Clusters
Infrared-Spectra
Dissociation-Energies
Electronic-Structures
Catalytic Co Oxidation
Gas-Phase Reactions
Lanthanide Metal-Clusters
Structural-Characterization
Ionization-Potentials
Threshold Photoionization
url http://hdl.handle.net/20.500.11937/12479