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• W4239432992 endingPage "1822" @default.
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• W4239432992 abstract "The gas phase ion chemistry of phosphine has been investigated by ab initio theoretical calculations and experimental techniques. Following previous studies dealing with P+3 and PH+ reacting with PH3, the quantum chemical study of these processes has been extended to the ion/molecule reactions starting from PH2+ and PH3 (reaction a) or PH3+ and PH3 (reaction b), as observed by ion trapping. In these experiments, PH2+ reacts to give P2Hn+ (n=1,3) product ions, with loss of H2 through different pathways. These processes take place at quite different rates, their constants being 2.6 and 7.6×10−10 cm3 molecule−1 s−1, respectively. The geometrical structures and energies of transition structures, reaction intermediates, and final products have been determined by ab initio theoretical methods. The initial step of the reaction of PH2+ with PH3 is formation of the H2P–PH3+ adduct. Then, a hydrogen molecule can be directly lost either from tricoordinated or tetracoordinated phosphorus, to give P–PH3+ or HP=PH2+, respectively. The shift of one H atom in HP=PH2+ produces the bridged HP(H)PH+ ion, from which further dissociation of H2 yields PPH+. The initial step of the reaction of PH3+ with PH3 is formation of the H3P–PH3+ adduct. Then inversion of the H atoms in the PH3 group transforms the adduct in an electrostatic complex. This last species is related by a dissociation process to the PH2 and PH4+ products. The heats of formation of the P2Hn+ (n=1–6) ionic species have been computed and compared with the experimental data in the literature." @default.
• W4239432992 created "2022-05-12" @default.
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• W4239432992 date "2000-01-22" @default.
• W4239432992 modified "2023-10-11" @default.
• W4239432992 title "Gas phase ion chemistry and <i>ab initio</i> theoretical study of phosphine. III. Reactions of PH2+ and PH3+ with PH3" @default.
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• W4239432992 doi "https://doi.org/10.1063/1.480745" @default.
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