Electron attachment to Ni(PF{sub 3}){sub 4} and Pt(PF{sub 3}){sub 4}

Journal Article · Fri Mar 14 04:00:00 EDT 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2831391· OSTI ID:21103999

Friedman, Jeffrey F; Miller, Thomas M; Friedman-Schaffer, Jessica K ^[1]; Rekha, G K; Stevens, Amy E ^[1]; Viggiano, A A

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1. Air Force Research Laboratory, Space Vehicles Directorate, Hanscom Air Force Base, Bedford, Massachusetts 01731-3010 (United States)

An experimental study has been made of thermal electron attachment to the transition-metal trifluorophosphine complexes Ni(PF{sub 3}){sub 4} and Pt(PF{sub 3}){sub 4} using a flowing-afterglow Langmuir-probe apparatus. Both complexes are efficient at electron attachment, although the rate constants are somewhat less than collisional. The rate constant for electron attachment to Ni(PF{sub 3}){sub 4} is 1.9x10{sup -7} cm{sup 3} s{sup -1} at room temperature, about a factor of 2 less than collisional. The activation energy is 39{+-}5 meV for the attachment reaction. The rate constant for electron attachment to Pt(PF{sub 3}){sub 4} is 5.4x10{sup -8} cm{sup 3} s{sup -1} at room temperature, and the activation energy is 84{+-}8 meV. For both complexes, a PF{sub 3} ligand is lost on electron attachment, and only the M(PF{sub 3}){sub 3}{sup -} ion is observed in the negative-ion mass spectrum. Density functional calculations were carried out on Ni(PF{sub 3}){sub 4} and various fragments in order to describe the thermochemistry of the attachment reaction.

• OSTI ID: 21103999
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 10 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANIONS
CHEMICAL ANALYSIS
DENSITY FUNCTIONAL METHOD
ELECTRON ATTACHMENT
MASS SPECTRA
NICKEL COMPLEXES
PLATINUM COMPLEXES
REACTION KINETICS
TEMPERATURE RANGE 0273-0400 K