A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus

• Main Authors: Wang, Lee-Ping (Author), Tofan, Daniel (Contributor), Chen, Jiahao (Contributor), Van Voorhis, Troy (Contributor), Cummins, Christopher C. (Contributor)
• Other Authors: Massachusetts Institute of Technology. Computer Science and Artificial Intelligence Laboratory (Contributor), Massachusetts Institute of Technology. Department of Chemistry (Contributor)
• Format: Article
• Language: English
• Published: Royal Society of Chemistry, 2014-10-20T12:46:55Z.
• Subjects: Article
• Online Access: Get fulltext

 We report a computational study of an energetically favorable pathway for the excited-state dissociation of a tetrahedral P[subscript 4] molecule into two P[subscript 2] molecules via the simultaneous breaking of four chemical bonds along a highly symmetric (D[subscript 2d]) reaction pathway. Along this pathway, a degeneracy occurs between the first excited state of P[subscript 4] and the ground state of 2P[subscript 2] 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.