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Issue 45, 2013
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A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus

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Abstract

We report a computational study of an energetically favorable pathway for the excited-state dissociation of a tetrahedral P4 molecule into two P2 molecules via the simultaneous breaking of four chemical bonds along a highly symmetric (D2d) reaction pathway. Along this pathway, a degeneracy occurs between the first excited state of P4 and the ground state of 2P2 at a lower total energy (ca. 4.7 eV) than the initial state, indicating that the initial photoexcitation provides sufficient energy for the dissociation without significant kinetic barriers. We also found that sequential dissociation of the four P–P bonds exhibits larger activation barriers thus making this a less viable dissociation pathway. Our computational investigation uncovers complicated photochemistry in elemental phosphorus, and suggests a likely mechanism for the environmentally friendly inclusion of phosphorus atoms into organic molecules.

Graphical abstract: A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus

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Publication details

The article was received on 26 Jul 2013, accepted on 23 Sep 2013 and first published on 25 Sep 2013


Article type: Paper
DOI: 10.1039/C3RA43940B
Citation: RSC Adv., 2013,3, 23166-23171
  • Open access: Creative Commons BY license
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    A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus

    L. Wang, D. Tofan, J. Chen, T. Van Voorhis and C. C. Cummins, RSC Adv., 2013, 3, 23166
    DOI: 10.1039/C3RA43940B

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