Direct Determination of the Ionization Energies of PtC, PtO, and PtO2 with VUVRadiation [electronic resource].
- Berkeley, Calif. : Lawrence Berkeley National Laboratory, 2008.
Oak Ridge, Tenn. : Distributed by the Office of Scientific and Technical Information, U.S. Dept. of Energy.
- Physical Description:
- 7 : digital, PDF file
- Additional Creators:
- Lawrence Berkeley National Laboratory
United States. Department of Energy. Office of Scientific and Technical Information
- 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.
- Published through SciTech Connect.
The Journal of Physical Chemistry A 112 FT
Ahmed, Musahid; Metz, Ricardo B.; Belau, Leonid; Citir, Murat.
Chemical Sciences Division
- Funding Information:
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