A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus
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...
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| Format: | Article |
| Language: | en_US |
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Royal Society of Chemistry
2014
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| Online Access: | http://hdl.handle.net/1721.1/90977 https://orcid.org/0000-0003-2568-3269 https://orcid.org/0000-0001-7111-0176 |
| _version_ | 1826208894533238784 |
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| author | Wang, Lee-Ping Tofan, Daniel Chen, Jiahao Van Voorhis, Troy Cummins, Christopher C. |
| author2 | Massachusetts Institute of Technology. Computer Science and Artificial Intelligence Laboratory |
| author_facet | Massachusetts Institute of Technology. Computer Science and Artificial Intelligence Laboratory Wang, Lee-Ping Tofan, Daniel Chen, Jiahao Van Voorhis, Troy Cummins, Christopher C. |
| author_sort | Wang, Lee-Ping |
| collection | MIT |
| description | 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. |
| first_indexed | 2024-09-23T14:14:00Z |
| format | Article |
| id | mit-1721.1/90977 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:14:00Z |
| publishDate | 2014 |
| publisher | Royal Society of Chemistry |
| record_format | dspace |
| spelling | mit-1721.1/909772022-09-28T19:22:22Z A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus Wang, Lee-Ping Tofan, Daniel Chen, Jiahao Van Voorhis, Troy Cummins, Christopher C. Massachusetts Institute of Technology. Computer Science and Artificial Intelligence Laboratory Massachusetts Institute of Technology. Department of Chemistry Tofan, Daniel Chen, Jiahao Van Voorhis, Troy Cummins, Christopher C. 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. National Science Foundation (U.S.) (Grant CHE-6923295) National Science Foundation (U.S.) (Grant CHE-1111357) 2014-10-20T12:46:55Z 2014-10-20T12:46:55Z 2013-09 2013-07 Article http://purl.org/eprint/type/JournalArticle 2046-2069 http://hdl.handle.net/1721.1/90977 Wang, Lee-Ping, Daniel Tofan, Jiahao Chen, Troy Van Voorhis, and Christopher C. Cummins. “A Pathway to Diphosphorus from the Dissociation of Photoexcited Tetraphosphorus.” RSC Adv. 3, no. 45 (2013): 23166. © The Royal Society of Chemistry https://orcid.org/0000-0003-2568-3269 https://orcid.org/0000-0001-7111-0176 en_US http://dx.doi.org/10.1039/c3ra43940b RSC Advances Creative Commons Attribution http://creativecommons.org/licenses/by/3.0/ application/pdf Royal Society of Chemistry RSC |
| spellingShingle | Wang, Lee-Ping Tofan, Daniel Chen, Jiahao Van Voorhis, Troy Cummins, Christopher C. A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title | A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title_full | A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title_fullStr | A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title_full_unstemmed | A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title_short | A pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| title_sort | pathway to diphosphorus from the dissociation of photoexcited tetraphosphorus |
| url | http://hdl.handle.net/1721.1/90977 https://orcid.org/0000-0003-2568-3269 https://orcid.org/0000-0001-7111-0176 |
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