Direct Determination of the Ionization Energies of PtC, PtO, and PtO2 with VUVRadiation

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Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements providethe first directly measured ionization energy for PtC, IE(PtC) = 9.45 +- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +- 0.1 eV and IE(PtO2) = 11.35 +- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly ... continued below

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Citir, Murat; Metz, Ricardo B.; Belau, Leonid & Ahmed, Musahid July 21, 2008.

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Photoionization efficiency curves were measured for gas-phase PtC, PtO, and PtO2 using tunable vacuum ultraviolet (VUV) radiation at the Advanced Light Source. The molecules were prepared by laser ablation of a platinum tube, followed by reaction with CH4 or N2O and supersonic expansion. These measurements providethe first directly measured ionization energy for PtC, IE(PtC) = 9.45 +- 0.05 eV. The direct measurement also gives greatly improved ionization energies for the platinum oxides, IE(PtO) = 10.0 +- 0.1 eV and IE(PtO2) = 11.35 +- 0.05 eV. The ionization energy connects the dissociation energies of the neutral and cation, leading to greatly improved 0 K bond dissociation energies for the neutrals: D0(Pt-C) = 5.95 +- 0.07 eV, D0(Pt-O)= 4.30 +- 0.12 eV, and D0(OPt-O) = 4.41 +- 0.13 eV, as well as enthalpies of formation for the gas-phase molecules Delta H0 f,0(PtC(g)) = 701 +- 7 kJ/mol, Delta H0f,0(PtO(g)) = 396 +- 12 kJ/mol, and Delta H0f,0(PtO2(g)) = 218 +- 11 kJ/mol. Much of the error in previous Knudsen cell measurements of platinum oxide bond dissociation energies is due to the use of thermodynamic second law extrapolations. Third law values calculated using statistical mechanical thermodynamic functions are in much better agreement with values obtained from ionization energies and ion energetics. These experiments demonstrate that laser ablation production with direct VUV ionization measurements is a versatile tool to measure ionization energies and bond dissociation energies for catalytically interesting species such as metal oxides and carbides.

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  • Journal Name: The Journal of Physical Chemistry A; Journal Volume: 112; Related Information: Journal Publication Date: 2008

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  • Report No.: LBNL-1231E
  • Grant Number: DE-AC02-05CH11231
  • Office of Scientific & Technical Information Report Number: 943969
  • Archival Resource Key: ark:/67531/metadc896694

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  • July 21, 2008

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  • Sept. 27, 2016, 1:39 a.m.

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  • Oct. 3, 2016, 1:45 p.m.

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Citir, Murat; Metz, Ricardo B.; Belau, Leonid & Ahmed, Musahid. Direct Determination of the Ionization Energies of PtC, PtO, and PtO2 with VUVRadiation, article, July 21, 2008; Berkeley, California. (digital.library.unt.edu/ark:/67531/metadc896694/: accessed October 18, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT Libraries Government Documents Department.