- The P(4Su) + N3(2Πg) Reaction: Chemical Generation of a New Metastable State of PN
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The kinetics and spectroscopy of the chemiluminescent reaction between P(4Su) atoms and N3(2Πg) radicals were studied with a discharge-flow apparatus.The chemiluminescence exhibited three band systems, which were identified as PN (A1Π -> X1Σ+), PF (B3Π -> X3Σ-), and a previoiusly unobserved system in PN.From the spectrum of the new system, molecular constants of the excited state were found to be Te = 25863 +/- 16 cm-1, ω'e = 957 +/- 8 cm-1, and ωeX'e = 18 +/- 2 cm-1.This excited state appears to be significantly Franck-Condon shifted from the ground state, with 0.3 being the most intense band of the spectrum.From comparison of this system with the analogous N(4Su) + N3(2Πg) reaction, the new excited state of PN is expected to be a triplet metastable, either a3Π or a'3Σ+.Analysis of the time behavior of the removal of P atoms from the system indicated a rate constant of (4.7 +/- 0.4)E-11 cm3 s-1 for the P + N reaction.The lifetime of the excited metastable state of PN is greater than 4 ms.
- Henshaw, T. L.,MacDonald, M. A.,Stedman, D. H.,Coombe, R. D.
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- Experimental observation of the 16-electron molecules SPN, SNP, and cyclic PSN
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16-Electron triatomic ring: Novel thiazylidynephosphane (SNP) was produced by either flash vacuum pyrolysis (ca. 1000 °C) or laser photolysis (193 nm) of SP(N3)3. Its photointerconversion to cyclic thiazaphosphirine (cyc-PSN) and thiophosphoryl nitride (SPN) was found in Ar matrix at 16 K. Cyc-PSN is the first experimentally observed 16-electron cyclic triatomic molecule. Copyright
- Zeng, Xiaoqing,Beckers, Helmut,Willner, Helge,Francisco, Joseph S.
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p. 3334 - 3339
(2012/06/15)
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- Phosphorus(V) nitride α-P3N5: Synthesis starting from tetraaminophosphonium iodide and crystal structure determination by synchrotron powder diffraction
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Pure phosphorus(V) nitride α-P3N5 was synthesized by thermal condensation of tetraaminophosphonium iodide [P(NH2)4]I at 825°C as a fine crystalline solid. The crystal structure was solved by direct methods and refined by a Rietveld algorithm on the basis of synchrotron powder diffraction data obtained at the ESRF, Grenoble, on beam-line BM1 (α-P3N5, Cc, a = 812.077(4), b = 583.433(4), c = 916.005(5) pm, β = 115.809(1)°, Z = 4, 699 observed reflections, wRp = 0.113, Rp = 0.091, RF = 0.060). With the same topology of the P-N network structure and similar R values the crystal structure may also be described with space group C2/c. In solid α-P3N5 there are PN4 tetrahedra which are connected through common edges and corners. Two out of five nitrogen each are bridging three and the remaining N are bridging two neighbouring P atoms. In a nonoxidizing atmosphere α-P3N5 is stable up to 800°C. Furthermore the compound is insoluble in all common solvents and resistant against hot acids and alkaline solutions.
- Horstmann, Stefan,Irran, Elisabeth,Schnick, Wolfgang
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p. 620 - 628
(2008/10/09)
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- The stability of PN and (PN)3. Ab initio calculations and matrix infrared investigations
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A new method of generating the high-temperature molecule PN is described. Previous results for the decomposition of PN into P2 and N2 as well as for the formation and properties of (PN)3 are confirmed. The reaction energy
- Ahlrichs, Reinhart,Baer, Michael,Plitt, Harald S.,Schnoeckel, Hansgeorg
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p. 179 - 184
(2008/10/08)
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