Oxidation pathways in the reaction of diacetylene with OH radicals
We present a portion of the potential energy surface of the reaction of diacetylene with OH radicals, calculated using RQCISD(T) and two basis set extrapolation schemes. Based on this surface, we performed calculations of the rate coefficients using an RRKM/master-equation formalism. After a small (...
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| Veröffentlicht in: | Proceedings of the Combustion Institute 2007, Vol.31 (1), p.185-192 |
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| creator | Senosiain, Juan P. Klippenstein, Stephen J. Miller, James A. |
| description | We present a portion of the potential energy surface of the reaction of diacetylene with OH radicals, calculated using RQCISD(T) and two basis set extrapolation schemes. Based on this surface, we performed calculations of the rate coefficients using an RRKM/master-equation formalism. After a small (1
kcal/mol) adjustment to the energy barrier of the association reaction, our calculated rate coefficients of the high-pressure limit agree very well with previous direct measurements. However, our calculations at high temperatures are considerably smaller than the values inferred in previous studies. The non-Arrhenius behavior and significant pressure dependence of the rate coefficients above 800
K is due to the competition between stabilization, abstraction and addition–elimination channels. At low temperatures, the reaction proceeds mostly to the addition products, as well as to CO and propargyl. Above 1200
K, direct hydrogen abstraction and production of H atoms become important. |
| doi_str_mv | 10.1016/j.proci.2006.08.084 |
| format | Article |
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kcal/mol) adjustment to the energy barrier of the association reaction, our calculated rate coefficients of the high-pressure limit agree very well with previous direct measurements. However, our calculations at high temperatures are considerably smaller than the values inferred in previous studies. The non-Arrhenius behavior and significant pressure dependence of the rate coefficients above 800
K is due to the competition between stabilization, abstraction and addition–elimination channels. At low temperatures, the reaction proceeds mostly to the addition products, as well as to CO and propargyl. Above 1200
K, direct hydrogen abstraction and production of H atoms become important.</description><identifier>ISSN: 1540-7489</identifier><identifier>EISSN: 1873-2704</identifier><identifier>DOI: 10.1016/j.proci.2006.08.084</identifier><language>eng</language><publisher>United States: Elsevier Inc</publisher><subject>08 HYDROGEN ; ATOMS ; Carbon monoxide ; Channels ; COMBUSTION ; Diacetylene ; EXTRAPOLATION ; Formalism ; HYDROGEN ; Hydroxyl ; Master equation ; Mathematical analysis ; OXIDATION ; POTENTIAL ENERGY ; PRESSURE DEPENDENCE ; PRODUCTION ; RADICALS ; Soot ; STABILIZATION</subject><ispartof>Proceedings of the Combustion Institute, 2007, Vol.31 (1), p.185-192</ispartof><rights>2006 The Combustion Institute</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c361t-78d3c1b82e281cfbd23de015436c466b0b9b66169a1ee68c59c539dab6242a493</citedby><cites>FETCH-LOGICAL-c361t-78d3c1b82e281cfbd23de015436c466b0b9b66169a1ee68c59c539dab6242a493</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktohtml>$$Uhttps://www.sciencedirect.com/science/article/pii/S1540748906003476$$EHTML$$P50$$Gelsevier$$H</linktohtml><link.rule.ids>309,314,776,780,881,3537,4010,27900,27901,27902,65306</link.rule.ids><backlink>$$Uhttps://www.osti.gov/biblio/971913$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Senosiain, Juan P.</creatorcontrib><creatorcontrib>Klippenstein, Stephen J.</creatorcontrib><creatorcontrib>Miller, James A.</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States)</creatorcontrib><title>Oxidation pathways in the reaction of diacetylene with OH radicals</title><title>Proceedings of the Combustion Institute</title><description>We present a portion of the potential energy surface of the reaction of diacetylene with OH radicals, calculated using RQCISD(T) and two basis set extrapolation schemes. Based on this surface, we performed calculations of the rate coefficients using an RRKM/master-equation formalism. After a small (1
kcal/mol) adjustment to the energy barrier of the association reaction, our calculated rate coefficients of the high-pressure limit agree very well with previous direct measurements. However, our calculations at high temperatures are considerably smaller than the values inferred in previous studies. The non-Arrhenius behavior and significant pressure dependence of the rate coefficients above 800
K is due to the competition between stabilization, abstraction and addition–elimination channels. At low temperatures, the reaction proceeds mostly to the addition products, as well as to CO and propargyl. Above 1200
K, direct hydrogen abstraction and production of H atoms become important.</description><subject>08 HYDROGEN</subject><subject>ATOMS</subject><subject>Carbon monoxide</subject><subject>Channels</subject><subject>COMBUSTION</subject><subject>Diacetylene</subject><subject>EXTRAPOLATION</subject><subject>Formalism</subject><subject>HYDROGEN</subject><subject>Hydroxyl</subject><subject>Master equation</subject><subject>Mathematical analysis</subject><subject>OXIDATION</subject><subject>POTENTIAL ENERGY</subject><subject>PRESSURE DEPENDENCE</subject><subject>PRODUCTION</subject><subject>RADICALS</subject><subject>Soot</subject><subject>STABILIZATION</subject><issn>1540-7489</issn><issn>1873-2704</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2007</creationdate><recordtype>article</recordtype><recordid>eNp9UEFOwzAQtBBIlMILuIQTpwQ7Th37wAEqoEiVeoGz5ay3qqs0KbZL6e9xG85IK81KOzOaHUJuGS0YZeJhXWx9D64oKRUFlWmqMzJisuZ5WdPqPO2TiuZ1JdUluQphTSmvKZ-MyPPix1kTXd9lWxNXe3MImeuyuMLMo4HToV9m1hnAeGixw2zv4ipbzDJvrAPThmtysUyAN384Jp-vLx_TWT5fvL1Pn-Y5cMFiXkvLgTWyxFIyWDa25BZpysUFVEI0tFGNEEwowxCFhImCCVfWNKKsSlMpPiZ3g28fotMBXERYQd91CFGrminGE-d-4KQ-vnYYot64ANi2psN-F7SUiksuT258YILvQ_C41FvvNsYfNKP6WKpe61Op-liqpjJNlVSPgwrTo98O_TEHdoDW-WMM27t_9b8ZvIBp</recordid><startdate>2007</startdate><enddate>2007</enddate><creator>Senosiain, Juan P.</creator><creator>Klippenstein, Stephen J.</creator><creator>Miller, James A.</creator><general>Elsevier Inc</general><general>Proc. Vol. 31, pp. 185-192</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><scope>OTOTI</scope></search><sort><creationdate>2007</creationdate><title>Oxidation pathways in the reaction of diacetylene with OH radicals</title><author>Senosiain, Juan P. ; Klippenstein, Stephen J. ; Miller, James A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c361t-78d3c1b82e281cfbd23de015436c466b0b9b66169a1ee68c59c539dab6242a493</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2007</creationdate><topic>08 HYDROGEN</topic><topic>ATOMS</topic><topic>Carbon monoxide</topic><topic>Channels</topic><topic>COMBUSTION</topic><topic>Diacetylene</topic><topic>EXTRAPOLATION</topic><topic>Formalism</topic><topic>HYDROGEN</topic><topic>Hydroxyl</topic><topic>Master equation</topic><topic>Mathematical analysis</topic><topic>OXIDATION</topic><topic>POTENTIAL ENERGY</topic><topic>PRESSURE DEPENDENCE</topic><topic>PRODUCTION</topic><topic>RADICALS</topic><topic>Soot</topic><topic>STABILIZATION</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Senosiain, Juan P.</creatorcontrib><creatorcontrib>Klippenstein, Stephen J.</creatorcontrib><creatorcontrib>Miller, James A.</creatorcontrib><creatorcontrib>Argonne National Lab. (ANL), Argonne, IL (United States)</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>OSTI.GOV</collection><jtitle>Proceedings of the Combustion Institute</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Senosiain, Juan P.</au><au>Klippenstein, Stephen J.</au><au>Miller, James A.</au><aucorp>Argonne National Lab. (ANL), Argonne, IL (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Oxidation pathways in the reaction of diacetylene with OH radicals</atitle><jtitle>Proceedings of the Combustion Institute</jtitle><date>2007</date><risdate>2007</risdate><volume>31</volume><issue>1</issue><spage>185</spage><epage>192</epage><pages>185-192</pages><issn>1540-7489</issn><eissn>1873-2704</eissn><abstract>We present a portion of the potential energy surface of the reaction of diacetylene with OH radicals, calculated using RQCISD(T) and two basis set extrapolation schemes. Based on this surface, we performed calculations of the rate coefficients using an RRKM/master-equation formalism. After a small (1
kcal/mol) adjustment to the energy barrier of the association reaction, our calculated rate coefficients of the high-pressure limit agree very well with previous direct measurements. However, our calculations at high temperatures are considerably smaller than the values inferred in previous studies. The non-Arrhenius behavior and significant pressure dependence of the rate coefficients above 800
K is due to the competition between stabilization, abstraction and addition–elimination channels. At low temperatures, the reaction proceeds mostly to the addition products, as well as to CO and propargyl. Above 1200
K, direct hydrogen abstraction and production of H atoms become important.</abstract><cop>United States</cop><pub>Elsevier Inc</pub><doi>10.1016/j.proci.2006.08.084</doi><tpages>8</tpages></addata></record> |
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| subjects | 08 HYDROGEN ATOMS Carbon monoxide Channels COMBUSTION Diacetylene EXTRAPOLATION Formalism HYDROGEN Hydroxyl Master equation Mathematical analysis OXIDATION POTENTIAL ENERGY PRESSURE DEPENDENCE PRODUCTION RADICALS Soot STABILIZATION |
| title | Oxidation pathways in the reaction of diacetylene with OH radicals |
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