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Ervin KM, Lineberger WC: Photoelectron spectroscopy of phosphorus hydride anions. J Chem Phys. 2005 May 15;122(19):194303.
Negative-ion photoelectron spectroscopy is applied to the PH-, PH2-, P2H-, P2H2-, and P2H3-molecular anions. Franck-Condon simulations of the photoelectron spectra are used to analyze the spectra and to identify various P2H (n)- species. The simulations employ density-functional theory calculations of molecular geometries and vibrational frequencies and normal modes, and coupled-cluster theory calculations of electron affinities. The following electron affinities are obtained: EA0 (PH) = 1.027 +/- 0.006 eV, EA0 (PH2) = 1.263 +/- 0.006 eV, and EA0 (P2H) = 1.514 +/- 0.010 eV. A band is identified as a mixture of trans-HPPH- and cis-HPPH-. Although the trans and cis bands cannot be definitively assigned from experimental information, using theory as a guide we obtain EA0 (trans-HPPH)= 1.00 +/- 0.01 eV and EA0 (cis-HPPH) = 1.03 +/- 0.01 eV. A weak feature tentatively assigned to P2H3- has a vertical detachment energy of 1.74 eV. The derived gas-phase acidity of phosphine is delta (acid) G298 (PH3) < or = 1509.7 +/- 2.1 kJ mo1 (-1). |
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