Direct determination of the ionization energies of PtC, PtO, and PtO2 with VUV radiation

The Journal of Physical Chemistry. a
Murat CitirMusahid Ahmed

Abstract

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 provide the 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 DeltaH(0)(f,0)(PtC(g)) = 701 +/- 7 kJ/mol, DeltaH(0)(f,0)(PtO(g)) = 396 +/- 12 kJ/mol, and DeltaH(0)(f,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 functi...Continue Reading

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Citations

Mar 17, 2016·Annual Review of Physical Chemistry·Oleg KostkoMusahid Ahmed
Aug 1, 2013·The Journal of Physical Chemistry. a·P B Armentrout, Feng-Xia Li
Apr 27, 2010·Physical Chemistry Chemical Physics : PCCP·Stephen R LeoneKevin R Wilson
Aug 1, 2020·Chemical Communications : Chem Comm·Ryo ToyoshimaHiroshi Kondoh
Aug 24, 2020·The Journal of Chemical Physics·Jason J SorensenMichael D Morse
Apr 9, 2021·Nature Communications·Christian Tantardini, Artem R Oganov
Jan 1, 2010·Chemical Reviews·Jana Roithová, Detlef Schröder
Jan 28, 2009·The Journal of Physical Chemistry. a·Oleg KostkoRicardo B Metz
Apr 2, 2009·The Journal of Physical Chemistry. a·Yu Gong, Mingfei Zhou
Sep 28, 2017·Journal of Chemical Theory and Computation·Yuri A AotoAntonio G S de Oliveira-Filho

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