Detailed kinetics of hydrogen abstraction from trans -decalin by OH radicals: the role of hindered internal rotation treatment
In this study, the detailed kinetic mechanism of the trans -decalin + OH reaction is firstly investigated for a wide range of conditions ( i.e. , T = 200–2000 K & P = 0.76–76 000 Torr) using the M06-2X/aug-cc-pVTZ level and stochastic Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME)...
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| Veröffentlicht in: | Physical chemistry chemical physics : PCCP 2020-11, Vol.22 (44), p.25740-25746 |
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| creator | Mai, Tam V.-T. Huynh, Lam K. |
| description | In this study, the detailed kinetic mechanism of the
trans
-decalin + OH reaction is firstly investigated for a wide range of conditions (
i.e.
,
T
= 200–2000 K &
P
= 0.76–76 000 Torr) using the M06-2X/aug-cc-pVTZ level and
stochastic
Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME) rate model, which includes corrections of the hindered internal rotor (HIR) and tunneling effects. Our predicted global rate constant excellently matches with the scarce experimental measurement (R. Atkinson,
et al. Int. J. Chem. Kinet.
, 1983,
15
, 37–50). The H-abstraction channel from C
α
of
trans
-decalin is found to be dominant at low temperatures. A U-shaped temperature-dependent behavior and slightly positive pressure-dependence at low temperatures (
e.g.
,
T
≤ 400 K &
P
= 760 Torr) of the total rate constants are also observed. Detailed analysis reveals that the HIR treatment is essential to capture the kinetic behavior while the tunneling correction only plays a minor role. |
| doi_str_mv | 10.1039/d0cp04314a |
| format | Article |
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trans
-decalin + OH reaction is firstly investigated for a wide range of conditions (
i.e.
,
T
= 200–2000 K &
P
= 0.76–76 000 Torr) using the M06-2X/aug-cc-pVTZ level and
stochastic
Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME) rate model, which includes corrections of the hindered internal rotor (HIR) and tunneling effects. Our predicted global rate constant excellently matches with the scarce experimental measurement (R. Atkinson,
et al. Int. J. Chem. Kinet.
, 1983,
15
, 37–50). The H-abstraction channel from C
α
of
trans
-decalin is found to be dominant at low temperatures. A U-shaped temperature-dependent behavior and slightly positive pressure-dependence at low temperatures (
e.g.
,
T
≤ 400 K &
P
= 760 Torr) of the total rate constants are also observed. Detailed analysis reveals that the HIR treatment is essential to capture the kinetic behavior while the tunneling correction only plays a minor role.</description><identifier>ISSN: 1463-9076</identifier><identifier>EISSN: 1463-9084</identifier><identifier>DOI: 10.1039/d0cp04314a</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Decalin ; Low temperature ; Pressure dependence ; Rate constants ; Temperature dependence</subject><ispartof>Physical chemistry chemical physics : PCCP, 2020-11, Vol.22 (44), p.25740-25746</ispartof><rights>Copyright Royal Society of Chemistry 2020</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c329t-89f52ae2037e9f5fca6ccc3a850f0c02fee7187c1cd388ca840b5e62d10f4a43</citedby><cites>FETCH-LOGICAL-c329t-89f52ae2037e9f5fca6ccc3a850f0c02fee7187c1cd388ca840b5e62d10f4a43</cites><orcidid>0000-0002-4310-2037 ; 0000-0002-3683-2787</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,780,784,27915,27916</link.rule.ids></links><search><creatorcontrib>Mai, Tam V.-T.</creatorcontrib><creatorcontrib>Huynh, Lam K.</creatorcontrib><title>Detailed kinetics of hydrogen abstraction from trans -decalin by OH radicals: the role of hindered internal rotation treatment</title><title>Physical chemistry chemical physics : PCCP</title><description>In this study, the detailed kinetic mechanism of the
trans
-decalin + OH reaction is firstly investigated for a wide range of conditions (
i.e.
,
T
= 200–2000 K &
P
= 0.76–76 000 Torr) using the M06-2X/aug-cc-pVTZ level and
stochastic
Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME) rate model, which includes corrections of the hindered internal rotor (HIR) and tunneling effects. Our predicted global rate constant excellently matches with the scarce experimental measurement (R. Atkinson,
et al. Int. J. Chem. Kinet.
, 1983,
15
, 37–50). The H-abstraction channel from C
α
of
trans
-decalin is found to be dominant at low temperatures. A U-shaped temperature-dependent behavior and slightly positive pressure-dependence at low temperatures (
e.g.
,
T
≤ 400 K &
P
= 760 Torr) of the total rate constants are also observed. Detailed analysis reveals that the HIR treatment is essential to capture the kinetic behavior while the tunneling correction only plays a minor role.</description><subject>Decalin</subject><subject>Low temperature</subject><subject>Pressure dependence</subject><subject>Rate constants</subject><subject>Temperature dependence</subject><issn>1463-9076</issn><issn>1463-9084</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNpdkU9LAzEQxYMoWP9c_AQBLyKsTjbZzdZbadUKhXrofUmzE5u6m9QkPfTiZ3fbigdP8x7zm8fAI-SGwQMDPnxsQG9AcCbUCRkwUfJsCJU4_dOyPCcXMa4BgBWMD8j3BJOyLTb00zpMVkfqDV3tmuA_0FG1jCkonax31ATf0d65SLMGtWqto8sdnU9pUI3tfXyiaYU0-BYPIdY1GPpk6xIGp9p-k9QhKgVUqUOXrsiZ6Q_x-ndeksXL82I8zWbz17fxaJZpng9TVg1NkSvMgUvspdGq1FpzVRVgQENuECWrpGa64VWlVSVgWWCZNwyMUIJfkrtj7Cb4ry3GVHc2amxb5dBvY52LQpZSCCl79PYfuvbb_fd7qmQiZwWwnro_Ujr4GAOaehNsp8KuZlDvm6gnMH4_NDHiP8lofP4</recordid><startdate>20201128</startdate><enddate>20201128</enddate><creator>Mai, Tam V.-T.</creator><creator>Huynh, Lam K.</creator><general>Royal Society of Chemistry</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>7X8</scope><orcidid>https://orcid.org/0000-0002-4310-2037</orcidid><orcidid>https://orcid.org/0000-0002-3683-2787</orcidid></search><sort><creationdate>20201128</creationdate><title>Detailed kinetics of hydrogen abstraction from trans -decalin by OH radicals: the role of hindered internal rotation treatment</title><author>Mai, Tam V.-T. ; Huynh, Lam K.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c329t-89f52ae2037e9f5fca6ccc3a850f0c02fee7187c1cd388ca840b5e62d10f4a43</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Decalin</topic><topic>Low temperature</topic><topic>Pressure dependence</topic><topic>Rate constants</topic><topic>Temperature dependence</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Mai, Tam V.-T.</creatorcontrib><creatorcontrib>Huynh, Lam K.</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>MEDLINE - Academic</collection><jtitle>Physical chemistry chemical physics : PCCP</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Mai, Tam V.-T.</au><au>Huynh, Lam K.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Detailed kinetics of hydrogen abstraction from trans -decalin by OH radicals: the role of hindered internal rotation treatment</atitle><jtitle>Physical chemistry chemical physics : PCCP</jtitle><date>2020-11-28</date><risdate>2020</risdate><volume>22</volume><issue>44</issue><spage>25740</spage><epage>25746</epage><pages>25740-25746</pages><issn>1463-9076</issn><eissn>1463-9084</eissn><abstract>In this study, the detailed kinetic mechanism of the
trans
-decalin + OH reaction is firstly investigated for a wide range of conditions (
i.e.
,
T
= 200–2000 K &
P
= 0.76–76 000 Torr) using the M06-2X/aug-cc-pVTZ level and
stochastic
Rice–Ramsperger–Kassel–Marcus based master equation (RRKM-ME) rate model, which includes corrections of the hindered internal rotor (HIR) and tunneling effects. Our predicted global rate constant excellently matches with the scarce experimental measurement (R. Atkinson,
et al. Int. J. Chem. Kinet.
, 1983,
15
, 37–50). The H-abstraction channel from C
α
of
trans
-decalin is found to be dominant at low temperatures. A U-shaped temperature-dependent behavior and slightly positive pressure-dependence at low temperatures (
e.g.
,
T
≤ 400 K &
P
= 760 Torr) of the total rate constants are also observed. Detailed analysis reveals that the HIR treatment is essential to capture the kinetic behavior while the tunneling correction only plays a minor role.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d0cp04314a</doi><tpages>7</tpages><orcidid>https://orcid.org/0000-0002-4310-2037</orcidid><orcidid>https://orcid.org/0000-0002-3683-2787</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1463-9076 |
| ispartof | Physical chemistry chemical physics : PCCP, 2020-11, Vol.22 (44), p.25740-25746 |
| issn | 1463-9076 1463-9084 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_2457674477 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Decalin Low temperature Pressure dependence Rate constants Temperature dependence |
| title | Detailed kinetics of hydrogen abstraction from trans -decalin by OH radicals: the role of hindered internal rotation treatment |
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