An ab initio spin-orbit-corrected potential energy surface and dynamics for the F + CH4 and F + CHD3 reactions
Identifieur interne : 006D48 ( Main/Exploration ); précédent : 006D47; suivant : 006D49An ab initio spin-orbit-corrected potential energy surface and dynamics for the F + CH4 and F + CHD3 reactions
Auteurs : Gabor Czako [États-Unis] ; Joel M. Bowman [États-Unis]Source :
- PCCP. Physical chemistry chemical physics : (Print) [ 1463-9076 ] ; 2011.
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Abstract
We report an analytical ab initio three degrees of freedom (3D) spin-orbit-correction surface for the entrance channel of the F + methane reaction obtained by fitting the differences between the spin-orbit (SO) and non-relativistic electronic ground state energies computed at the MRCI + Q/aug-cc-pVTZ level of theory. The 3D model surface is given in terms of the distance, R(C-F), and relative orientation, Euler angles φ and θ, of the reactants treating CH4 as a rigid rotor. The full-dimensional (12D) "hybrid" SO-corrected potential energy surface (PES) is obtained from the 3D SO-correction surface and a 12D non-SO PES. The SO interaction has a significant effect in the entrance-channel van der Waals region, whereas the effect on the energy at the early saddle point is only ∼5% of that at the reactant asymptote; thus, the SO correction increases the barrier height by ∼ 122 cm-1. The 12D quasiclassical trajectory calculations for the F + CH4 and F + CHD3 reactions show that the SO effects decrease the cross sections by a factor of 2-4 at low collision energies and the effects are less significant as the collision energy increases. The inclusion of the SO correction in the PES does not change the product state distributions.
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<record><TEI><teiHeader><fileDesc><titleStmt><title xml:lang="en" level="a">An ab initio spin-orbit-corrected potential energy surface and dynamics for the F + CH<sub>4</sub> and F + CHD<sub>3</sub> reactions</title><author><name sortKey="Czako, Gabor" sort="Czako, Gabor" uniqKey="Czako G" first="Gabor" last="Czako">Gabor Czako</name><affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Cherry L. Emerson Center for Scientific Contputation and Department of Chemistry, Emory University</s1><s2>Atlanta, GA 30322</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ></inist:fA14><country>États-Unis</country><wicri:noRegion>Atlanta, GA 30322</wicri:noRegion></affiliation></author><author><name sortKey="Bowman, Joel M" sort="Bowman, Joel M" uniqKey="Bowman J" first="Joel M." last="Bowman">Joel M. Bowman</name><affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Cherry L. Emerson Center for Scientific Contputation and Department of Chemistry, Emory University</s1><s2>Atlanta, GA 30322</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ></inist:fA14><country>États-Unis</country><wicri:noRegion>Atlanta, GA 30322</wicri:noRegion></affiliation></author></titleStmt><publicationStmt><idno type="wicri:source">INIST</idno><idno type="inist">11-0291033</idno><date when="2011">2011</date><idno type="stanalyst">PASCAL 11-0291033 INIST</idno><idno type="RBID">Pascal:11-0291033</idno><idno type="wicri:Area/PascalFrancis/Corpus">001B95</idno><idno type="wicri:Area/PascalFrancis/Curation">004349</idno><idno type="wicri:Area/PascalFrancis/Checkpoint">001D60</idno><idno type="wicri:explorRef" wicri:stream="PascalFrancis" wicri:step="Checkpoint">001D60</idno><idno type="wicri:doubleKey">1463-9076:2011:Czako G:an:ab:initio</idno><idno type="wicri:Area/Main/Merge">007211</idno><idno type="wicri:Area/Main/Curation">006D48</idno><idno type="wicri:Area/Main/Exploration">006D48</idno></publicationStmt><sourceDesc><biblStruct><analytic><title xml:lang="en" level="a">An ab initio spin-orbit-corrected potential energy surface and dynamics for the F + CH<sub>4</sub> and F + CHD<sub>3</sub> reactions</title><author><name sortKey="Czako, Gabor" sort="Czako, Gabor" uniqKey="Czako G" first="Gabor" last="Czako">Gabor Czako</name><affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Cherry L. Emerson Center for Scientific Contputation and Department of Chemistry, Emory University</s1><s2>Atlanta, GA 30322</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ></inist:fA14><country>États-Unis</country><wicri:noRegion>Atlanta, GA 30322</wicri:noRegion></affiliation></author><author><name sortKey="Bowman, Joel M" sort="Bowman, Joel M" uniqKey="Bowman J" first="Joel M." last="Bowman">Joel M. Bowman</name><affiliation wicri:level="1"><inist:fA14 i1="01"><s1>Cherry L. Emerson Center for Scientific Contputation and Department of Chemistry, Emory University</s1><s2>Atlanta, GA 30322</s2><s3>USA</s3><sZ>1 aut.</sZ><sZ>2 aut.</sZ></inist:fA14><country>États-Unis</country><wicri:noRegion>Atlanta, GA 30322</wicri:noRegion></affiliation></author></analytic><series><title level="j" type="main">PCCP. Physical chemistry chemical physics : (Print)</title><title level="j" type="abbreviated">PCCP, Phys. chem. chem. phys. : (Print)</title><idno type="ISSN">1463-9076</idno><imprint><date when="2011">2011</date></imprint></series></biblStruct></sourceDesc><seriesStmt><title level="j" type="main">PCCP. Physical chemistry chemical physics : (Print)</title><title level="j" type="abbreviated">PCCP, Phys. chem. chem. phys. : (Print)</title><idno type="ISSN">1463-9076</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Ab initio calculations</term><term>Collision energy</term><term>Cross section (collision)</term><term>Distribution</term><term>Dynamics</term><term>Ground state</term><term>Inclusion</term><term>Methane</term><term>Models</term><term>Orientation</term><term>Potential energy surfaces</term><term>Spin</term><term>Theoretical study</term><term>Theory</term><term>Trajectory</term></keywords><keywords scheme="Pascal" xml:lang="fr"><term>Calcul ab initio</term><term>Spin</term><term>Surface énergie potentielle</term><term>Dynamique</term><term>Méthane</term><term>Etude théorique</term><term>Etat fondamental</term><term>Energie collision</term><term>Théorie</term><term>Modèle</term><term>Orientation</term><term>Trajectoire</term><term>Section efficace</term><term>Inclusion</term><term>Distribution</term><term>3115A</term></keywords></textClass></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">We report an analytical ab initio three degrees of freedom (3D) spin-orbit-correction surface for the entrance channel of the F + methane reaction obtained by fitting the differences between the spin-orbit (SO) and non-relativistic electronic ground state energies computed at the MRCI + Q/aug-cc-pVTZ level of theory. The 3D model surface is given in terms of the distance, R(C-F), and relative orientation, Euler angles φ and θ, of the reactants treating CH<sub>4</sub> as a rigid rotor. The full-dimensional (12D) "hybrid" SO-corrected potential energy surface (PES) is obtained from the 3D SO-correction surface and a 12D non-SO PES. The SO interaction has a significant effect in the entrance-channel van der Waals region, whereas the effect on the energy at the early saddle point is only ∼5% of that at the reactant asymptote; thus, the SO correction increases the barrier height by ∼ 122 cm<sup>-1</sup>. The 12D quasiclassical trajectory calculations for the F + CH<sub>4</sub> and F + CHD<sub>3</sub> reactions show that the SO effects decrease the cross sections by a factor of 2-4 at low collision energies and the effects are less significant as the collision energy increases. The inclusion of the SO correction in the PES does not change the product state distributions.</div></front></TEI><affiliations><list><country><li>États-Unis</li></country></list><tree><country name="États-Unis"><noRegion><name sortKey="Czako, Gabor" sort="Czako, Gabor" uniqKey="Czako G" first="Gabor" last="Czako">Gabor Czako</name></noRegion><name sortKey="Bowman, Joel M" sort="Bowman, Joel M" uniqKey="Bowman J" first="Joel M." last="Bowman">Joel M. Bowman</name></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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