Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of OH Radicals with Dimethyl Ether
The reaction of OH with dimethyl ether (CH3OCH3) has been studied from 195 to 850 K using laser flash photolysis coupled to laser induced fluorescence detection of OH radicals. The rate coefficient from this work can be parametrized by the modified Arrhenius expression k = (1.23 ± 0.46) × 10–12 (T/2...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2013-11, Vol.117 (44), p.11142-11154 |
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| creator | Carr, S. A Still, T. J Blitz, M. A Eskola, A. J Pilling, M. J Seakins, P. W Shannon, R. J Wang, B Robertson, S. H |
| description | The reaction of OH with dimethyl ether (CH3OCH3) has been studied from 195 to 850 K using laser flash photolysis coupled to laser induced fluorescence detection of OH radicals. The rate coefficient from this work can be parametrized by the modified Arrhenius expression k = (1.23 ± 0.46) × 10–12 (T/298)2.05±0.23 exp((257 ± 107)/T) cm3 molecule–1 s–1. Including other recent literature data (923–1423 K) gives a modified Arrhenius expression of k 1 = (1.54 ± 0.48) × 10–12 (T/298 K)1.89±0.16 exp((184 ± 112)/T) cm3 molecule–1 s–1 over the range 195–1423 K. Various isotopomeric combinations of the reaction have also been investigated with deuteration of dimethyl ether leading to a normal isotope effect. Deuteration of the hydroxyl group leads to a small inverse isotope effect. To gain insight into the reaction mechanisms and to support the experimental work, theoretical studies have also been undertaken calculating the energies and structures of the transition states and complexes using high level ab initio methods. The calculations also identify pre- and post-reaction complexes. The calculations show that the pre-reaction complex has a binding energy of ∼22 kJ mol–1. Stabilization into the complex could influence the kinetics of the reaction, especially at low temperatures ( |
| doi_str_mv | 10.1021/jp4070278 |
| format | Article |
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A ; Still, T. J ; Blitz, M. A ; Eskola, A. J ; Pilling, M. J ; Seakins, P. W ; Shannon, R. J ; Wang, B ; Robertson, S. H</creator><creatorcontrib>Carr, S. A ; Still, T. J ; Blitz, M. A ; Eskola, A. J ; Pilling, M. J ; Seakins, P. W ; Shannon, R. J ; Wang, B ; Robertson, S. H</creatorcontrib><description>The reaction of OH with dimethyl ether (CH3OCH3) has been studied from 195 to 850 K using laser flash photolysis coupled to laser induced fluorescence detection of OH radicals. The rate coefficient from this work can be parametrized by the modified Arrhenius expression k = (1.23 ± 0.46) × 10–12 (T/298)2.05±0.23 exp((257 ± 107)/T) cm3 molecule–1 s–1. Including other recent literature data (923–1423 K) gives a modified Arrhenius expression of k 1 = (1.54 ± 0.48) × 10–12 (T/298 K)1.89±0.16 exp((184 ± 112)/T) cm3 molecule–1 s–1 over the range 195–1423 K. Various isotopomeric combinations of the reaction have also been investigated with deuteration of dimethyl ether leading to a normal isotope effect. Deuteration of the hydroxyl group leads to a small inverse isotope effect. To gain insight into the reaction mechanisms and to support the experimental work, theoretical studies have also been undertaken calculating the energies and structures of the transition states and complexes using high level ab initio methods. The calculations also identify pre- and post-reaction complexes. The calculations show that the pre-reaction complex has a binding energy of ∼22 kJ mol–1. Stabilization into the complex could influence the kinetics of the reaction, especially at low temperatures (<300 K), but there is no direct evidence of this occurring under the experimental conditions of this study. The experimental data have been modeled using the recently developed MESMER (master equation solver for multi energy well reactions) code; the calculated rate coefficients lie within 16% of the experimental values over the temperature range 200–1400 K with a model based on a single transition state. This model also qualitatively reproduces the observed isotope effects, agreeing closely above ∼600 K but overestimating them at low temperatures. The low temperature differences may derive from an inadequate treatment of tunnelling and/or from an enhanced role of an outer transition state leading to the pre-reaction complex.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp4070278</identifier><identifier>PMID: 24102528</identifier><language>eng</language><publisher>Washington, DC: American Chemical Society</publisher><subject>Ab initio calculations ; Atomic and molecular physics ; Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) ; Coefficients ; Deuteration ; Dimethyl ether ; Electronic structure of atoms, molecules and their ions: theory ; Energy use ; Exact sciences and technology ; Isotope effect ; Mathematical models ; Physics ; Radicals ; Reaction kinetics</subject><ispartof>The journal of physical chemistry. 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A</creatorcontrib><creatorcontrib>Still, T. J</creatorcontrib><creatorcontrib>Blitz, M. A</creatorcontrib><creatorcontrib>Eskola, A. J</creatorcontrib><creatorcontrib>Pilling, M. J</creatorcontrib><creatorcontrib>Seakins, P. W</creatorcontrib><creatorcontrib>Shannon, R. J</creatorcontrib><creatorcontrib>Wang, B</creatorcontrib><creatorcontrib>Robertson, S. H</creatorcontrib><title>Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of OH Radicals with Dimethyl Ether</title><title>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>The reaction of OH with dimethyl ether (CH3OCH3) has been studied from 195 to 850 K using laser flash photolysis coupled to laser induced fluorescence detection of OH radicals. The rate coefficient from this work can be parametrized by the modified Arrhenius expression k = (1.23 ± 0.46) × 10–12 (T/298)2.05±0.23 exp((257 ± 107)/T) cm3 molecule–1 s–1. Including other recent literature data (923–1423 K) gives a modified Arrhenius expression of k 1 = (1.54 ± 0.48) × 10–12 (T/298 K)1.89±0.16 exp((184 ± 112)/T) cm3 molecule–1 s–1 over the range 195–1423 K. Various isotopomeric combinations of the reaction have also been investigated with deuteration of dimethyl ether leading to a normal isotope effect. Deuteration of the hydroxyl group leads to a small inverse isotope effect. To gain insight into the reaction mechanisms and to support the experimental work, theoretical studies have also been undertaken calculating the energies and structures of the transition states and complexes using high level ab initio methods. The calculations also identify pre- and post-reaction complexes. The calculations show that the pre-reaction complex has a binding energy of ∼22 kJ mol–1. Stabilization into the complex could influence the kinetics of the reaction, especially at low temperatures (<300 K), but there is no direct evidence of this occurring under the experimental conditions of this study. The experimental data have been modeled using the recently developed MESMER (master equation solver for multi energy well reactions) code; the calculated rate coefficients lie within 16% of the experimental values over the temperature range 200–1400 K with a model based on a single transition state. This model also qualitatively reproduces the observed isotope effects, agreeing closely above ∼600 K but overestimating them at low temperatures. The low temperature differences may derive from an inadequate treatment of tunnelling and/or from an enhanced role of an outer transition state leading to the pre-reaction complex.</description><subject>Ab initio calculations</subject><subject>Atomic and molecular physics</subject><subject>Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations)</subject><subject>Coefficients</subject><subject>Deuteration</subject><subject>Dimethyl ether</subject><subject>Electronic structure of atoms, molecules and their ions: theory</subject><subject>Energy use</subject><subject>Exact sciences and technology</subject><subject>Isotope effect</subject><subject>Mathematical models</subject><subject>Physics</subject><subject>Radicals</subject><subject>Reaction kinetics</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2013</creationdate><recordtype>article</recordtype><recordid>eNqFkclOwzAQhi0EYj_wAsgXJDgExlucHFEpiwBVKnCOHMdWUrVJsR1B3x4HClyQOHmWz_-M_kHoiMA5AUouZksOEqjMNtAuERQSQYnYjDFkeSJSlu-gPe9nAEAY5dtoh_L4T9BsF_nx-9K4ZmHaoOZYtRV-rk3nTGh0zJ9CX61wZ3GoDb5v2qHsP6lHo2vVNn7x3Z0apUPTtUM-ucVTVQ0KHr81ocZXcUCoV3M8jqg7QFs2tszh-t1HL9fj59Ft8jC5uRtdPiSKySwkGRVlRUprS5vmMgWaai1yaSRhRMmyZBXjNMsgZSRjYIGTCoiljAIwKsGyfXT6pbt03WtvfCgWjddmPlet6XpfECkYzyXP2f8oj2CaCy4ievaFatd574wtltE_5VYFgWI4R_Fzjsger2X7cmGqH_Lb_wicrAHlo13WqVY3_peTw3qp_OWU9sWs610bjftj4AczTZuP</recordid><startdate>20131107</startdate><enddate>20131107</enddate><creator>Carr, S. A</creator><creator>Still, T. J</creator><creator>Blitz, M. A</creator><creator>Eskola, A. J</creator><creator>Pilling, M. J</creator><creator>Seakins, P. W</creator><creator>Shannon, R. J</creator><creator>Wang, B</creator><creator>Robertson, S. H</creator><general>American Chemical Society</general><scope>IQODW</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20131107</creationdate><title>Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of OH Radicals with Dimethyl Ether</title><author>Carr, S. A ; Still, T. J ; Blitz, M. A ; Eskola, A. J ; Pilling, M. J ; Seakins, P. W ; Shannon, R. J ; Wang, B ; Robertson, S. 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A</creatorcontrib><creatorcontrib>Still, T. J</creatorcontrib><creatorcontrib>Blitz, M. A</creatorcontrib><creatorcontrib>Eskola, A. J</creatorcontrib><creatorcontrib>Pilling, M. J</creatorcontrib><creatorcontrib>Seakins, P. W</creatorcontrib><creatorcontrib>Shannon, R. J</creatorcontrib><creatorcontrib>Wang, B</creatorcontrib><creatorcontrib>Robertson, S. H</creatorcontrib><collection>Pascal-Francis</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</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><jtitle>The journal of physical chemistry. 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A</addtitle><date>2013-11-07</date><risdate>2013</risdate><volume>117</volume><issue>44</issue><spage>11142</spage><epage>11154</epage><pages>11142-11154</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>The reaction of OH with dimethyl ether (CH3OCH3) has been studied from 195 to 850 K using laser flash photolysis coupled to laser induced fluorescence detection of OH radicals. The rate coefficient from this work can be parametrized by the modified Arrhenius expression k = (1.23 ± 0.46) × 10–12 (T/298)2.05±0.23 exp((257 ± 107)/T) cm3 molecule–1 s–1. Including other recent literature data (923–1423 K) gives a modified Arrhenius expression of k 1 = (1.54 ± 0.48) × 10–12 (T/298 K)1.89±0.16 exp((184 ± 112)/T) cm3 molecule–1 s–1 over the range 195–1423 K. Various isotopomeric combinations of the reaction have also been investigated with deuteration of dimethyl ether leading to a normal isotope effect. Deuteration of the hydroxyl group leads to a small inverse isotope effect. To gain insight into the reaction mechanisms and to support the experimental work, theoretical studies have also been undertaken calculating the energies and structures of the transition states and complexes using high level ab initio methods. The calculations also identify pre- and post-reaction complexes. The calculations show that the pre-reaction complex has a binding energy of ∼22 kJ mol–1. Stabilization into the complex could influence the kinetics of the reaction, especially at low temperatures (<300 K), but there is no direct evidence of this occurring under the experimental conditions of this study. The experimental data have been modeled using the recently developed MESMER (master equation solver for multi energy well reactions) code; the calculated rate coefficients lie within 16% of the experimental values over the temperature range 200–1400 K with a model based on a single transition state. This model also qualitatively reproduces the observed isotope effects, agreeing closely above ∼600 K but overestimating them at low temperatures. The low temperature differences may derive from an inadequate treatment of tunnelling and/or from an enhanced role of an outer transition state leading to the pre-reaction complex.</abstract><cop>Washington, DC</cop><pub>American Chemical Society</pub><pmid>24102528</pmid><doi>10.1021/jp4070278</doi><tpages>13</tpages></addata></record> |
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| ispartof | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory, 2013-11, Vol.117 (44), p.11142-11154 |
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| subjects | Ab initio calculations Atomic and molecular physics Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Coefficients Deuteration Dimethyl ether Electronic structure of atoms, molecules and their ions: theory Energy use Exact sciences and technology Isotope effect Mathematical models Physics Radicals Reaction kinetics |
| title | Experimental and Theoretical Study of the Kinetics and Mechanism of the Reaction of OH Radicals with Dimethyl Ether |
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