Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics
The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channe...
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Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2022-07, Vol.126 (29), p.4747-4761 |
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creator | Turner, Andrew M. Luo, Yuheng Marks, Joshua H. Sun, Rui Lechner, Jasmin T. Klapötke, Thomas M. Kaiser, Ralf I. |
description | The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by ONO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds. |
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Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by ONO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/acs.jpca.2c02696</identifier><identifier>PMID: 35852300</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters</subject><ispartof>The journal of physical chemistry. 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A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by ONO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds.</description><subject>A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2022</creationdate><recordtype>article</recordtype><recordid>eNp1kUtv1DAUhSMEoqWwZ4W8LFI8-BEn8RL6gEpVixiQ2EWOfcO4SuxgOxLDD-J34jADO1a-ss45V_d8RfGSkg0ljL5ROm4eZq02TBNWy_pRcUoFI1gwKh7nmbQSi5rLk-JZjA-EEMpZ9bQ44aIVjBNyWvy6-jGPPlj3DaUdoI87n7zewWRjCnvkB7T1ozWIlhRfWjVZ5zErGTbW2RQ8pN1-BAfo_Pr-K25eo-2snFvDtnaaR0DvvDPo0zKnJUAs0d1qwsnjdbAJ0E30EwT7UyXrXYlUVt95p4xVff7S6HLv8lIdnxdPBjVGeHF8z4ov11efLz7g2_v3Nxdvb7HivE544BqIqWQtakGV7ClUVQVNrygYKYdWDKI1HHIlfdOIXjMjNat1M9RSNEYN_Kw4P-TOwX9fIKYuN6FhHJUDv8Qul0ybVhLRZik5SHXwMQYYujnYSYV9R0m30ukynW6l0x3pZMurY_rST2D-Gf7iyILyIPhj9Utw-dj_5_0GReOdQA</recordid><startdate>20220728</startdate><enddate>20220728</enddate><creator>Turner, Andrew M.</creator><creator>Luo, Yuheng</creator><creator>Marks, Joshua H.</creator><creator>Sun, Rui</creator><creator>Lechner, Jasmin T.</creator><creator>Klapötke, Thomas M.</creator><creator>Kaiser, Ralf I.</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-7233-7206</orcidid><orcidid>https://orcid.org/0000-0002-3124-1179</orcidid><orcidid>https://orcid.org/0000-0003-0638-1353</orcidid></search><sort><creationdate>20220728</creationdate><title>Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics</title><author>Turner, Andrew M. ; Luo, Yuheng ; Marks, Joshua H. ; Sun, Rui ; Lechner, Jasmin T. ; Klapötke, Thomas M. ; Kaiser, Ralf I.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a336t-f3ce0d4965651a9b1e444e7ba1ed99f85f58d3e563b775bc2d9c26c7f6957daf3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>A: Structure, Spectroscopy, and Reactivity of Molecules and Clusters</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Turner, Andrew M.</creatorcontrib><creatorcontrib>Luo, Yuheng</creatorcontrib><creatorcontrib>Marks, Joshua H.</creatorcontrib><creatorcontrib>Sun, Rui</creatorcontrib><creatorcontrib>Lechner, Jasmin T.</creatorcontrib><creatorcontrib>Klapötke, Thomas M.</creatorcontrib><creatorcontrib>Kaiser, Ralf I.</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Turner, Andrew M.</au><au>Luo, Yuheng</au><au>Marks, Joshua H.</au><au>Sun, Rui</au><au>Lechner, Jasmin T.</au><au>Klapötke, Thomas M.</au><au>Kaiser, Ralf I.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2022-07-28</date><risdate>2022</risdate><volume>126</volume><issue>29</issue><spage>4747</spage><epage>4761</epage><pages>4747-4761</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>The UV photolysis of solid FOX-7 at 5 K with 355 and 532 nm photons was investigated to unravel initial isomerization and decomposition pathways. Isomer-selective single photon ionization coupled with reflectron time-of-flight mass spectrometry (ReTOF-MS) documented the nitric oxide (NO) loss channel at 355 nm along with a nitro-to-nitrite isomerization, which was observed by using infrared spectroscopy, representing the initial reaction pathway followed by ONO bond rupture of the nitrite moiety. A residual gas analyzer detected molecular oxygen for the 355 and 532 nm photolysis at a ratio of 4.3 ± 0.3:1, which signifies FOX-7 as an energetic material that provides its own oxidant once the decomposition starts. Overall branching ratios for molecular oxygen versus nitric oxide were derived to be 700 ± 100:1 at 355 nm. It is notable that this is the first time that molecular oxygen was detected as a decomposition product of FOX-7. Computations show that atomic oxygen, which later combines to form molecular oxygen, is likely released from a nitro group involving conical intersections. The condensed phase potential energy profile computed at the CCSD(T) and CASPT2 level correlates well with the experiments and highlights the critical roles of conical intersections, nonadiabatic dynamics, and the encapsulated environment that dictate the mechanism of the reaction through intermolecular hydrogen bonds.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>35852300</pmid><doi>10.1021/acs.jpca.2c02696</doi><tpages>15</tpages><orcidid>https://orcid.org/0000-0002-7233-7206</orcidid><orcidid>https://orcid.org/0000-0002-3124-1179</orcidid><orcidid>https://orcid.org/0000-0003-0638-1353</orcidid></addata></record> |
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title | Exploring the Photochemistry of Solid 1,1-Diamino-2,2-dinitroethylene (FOX-7) Spanning Simple Bond Ruptures, Nitro-to-Nitrite Isomerization, and Nonadiabatic Dynamics |
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