Predictive theory for the combination kinetics of two alkyl radicals

Physical Chemistry Chemical Physics : PCCP
Stephen J KlippensteinLawrence B Harding

Abstract

An ab initio transition state theory based procedure for accurately predicting the combination kinetics of two alkyl radicals is described. This procedure employs direct evaluations of the orientation dependent interaction energies at the CASPT2/cc-pvdz level within variable reaction coordinate transition state theory (VRC-TST). One-dimensional corrections to these energies are obtained from CAS+1+2/aug-cc-pvtz calculations for CH3 + CH3 along its combination reaction path. Direct CAS+1+2/aug-cc-pvtz calculations demonstrate that, at least for the purpose of predicting the kinetics, the corrected CASPT2/cc-pvdz potential energy surface is an accurate approximation to the CAS+1+2/aug-cc-pvtz surface. Furthermore, direct trajectory simulations, performed at the B3LYP/6-31G* level, indicate that there is little local recrossing of the optimal VRC transition state dividing surface. The corrected CASPT2/cc-pvdz potential is employed in obtaining direct VRC-TST kinetic predictions for the self and cross combinations of methyl, ethyl, iso-propyl, and tert-butyl radicals. Comparisons with experiment suggest that the present dynamically corrected VRC-TST approach provides quantitatively accurate predictions for the capture rate. Each ad...Continue Reading

References

Jan 7, 2005·The Journal of Chemical Physics·Attila TajtiJohn F Stanton
Sep 16, 2005·The Journal of Chemical Physics·Yuri Georgievskii, Stephen J Klippenstein
Jul 13, 2006·The Journal of Physical Chemistry. a·Lawrence B HardingStephen J Klippenstein
Jun 27, 2002·The Journal of Physical Chemistry. a·Regina J CodyLouis J Stief

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Citations

Feb 10, 2011·Faraday Discussions·Zhe PengPascal Pernot
Feb 10, 2011·Faraday Discussions·Roger V YelleJ Cui
Jan 15, 2009·The Journal of Chemical Physics·Hua-Chieh ShaoJim J Lin
Jun 13, 2015·The Journal of Physical Chemistry. a·Matthew K Sprague, Karl K Irikura
Dec 6, 2014·Science·Ahren W JasperStephen J Klippenstein
Nov 12, 2016·Proceedings of the National Academy of Sciences of the United States of America·Junwei Lucas BaoDonald G Truhlar
Nov 23, 2017·Chemical Society Reviews·Junwei Lucas Bao, Donald G Truhlar
Aug 10, 2007·Physical Chemistry Chemical Physics : PCCP·Yuri GeorgievskiiStephen J Klippenstein
Aug 10, 2007·Physical Chemistry Chemical Physics : PCCP·Adam M KneppStephen J Klippenstein
Aug 10, 2007·Physical Chemistry Chemical Physics : PCCP·Lawrence B HardingAhren W Jasper
Nov 19, 2008·Physical Chemistry Chemical Physics : PCCP·Matthew J AlmondRobin Walsh
Dec 22, 2019·Scientific Reports·Kun LiQiang Song
Apr 11, 2009·Chemistry : a European Journal·Zhen HuangRoman Boulatov
Dec 8, 2011·Physical Chemistry Chemical Physics : PCCP·Joshua W AllenWilliam H Green
Mar 16, 2019·Scientific Reports·Mohamed A Abdel-RahmanAhmed M El-Nahas
Aug 14, 2020·Physical Chemistry Chemical Physics : PCCP·John B RandazzoRobert S Tranter
May 22, 2013·Physical Chemistry Chemical Physics : PCCP·Judit ZádorCraig A Taatjes
Aug 3, 2018·The Journal of Chemical Physics·Chenchen Song, Todd J Martínez
Oct 1, 2011·Physical Chemistry Chemical Physics : PCCP·Jim J Lin
Aug 22, 2008·The Journal of Physical Chemistry. a·K L GannonL B Harding
May 22, 2008·The Journal of Physical Chemistry. a·Stig R SellevågJames A Miller
Dec 30, 2009·The Journal of Physical Chemistry. a·Lawrence B HardingStephen J Klippenstein
Jul 14, 2009·The Journal of Physical Chemistry. a·Sandeep Sharma, William H Green
Jan 17, 2009·The Journal of Physical Chemistry. a·Huzeifa IsmailCraig A Taatjes
Feb 4, 2010·The Journal of Physical Chemistry. a·James A MillerAndrew C Simmonett
Nov 10, 2006·Chemical Reviews·Antonio Fernandez-RamosDonald G Truhlar
Feb 25, 2009·Journal of the American Chemical Society·Maria BesoraMichael Towrie
Apr 18, 2009·The Journal of Physical Chemistry. a·Stig R SellevågJames A Miller
Oct 28, 2008·The Journal of Physical Chemistry. a·Jingjing ZhengDonald G Truhlar
Oct 28, 2009·The Journal of Physical Chemistry. a·Stephen J KlippensteinBenjamin J McCall
Dec 19, 2008·The Journal of Physical Chemistry. a·Hans-Heinrich Carstensen, Anthony M Dean
Jul 3, 2009·The Journal of Physical Chemistry. a·Xueliang YangRobert S Tranter
Aug 13, 2010·The Journal of Physical Chemistry. a·Robert S TranterJohn H Kiefer
Aug 13, 2010·The Journal of Physical Chemistry. a·Rex T SkodjeMichael J Davis
Jun 16, 2021·The Journal of Physical Chemistry. a·Balla RajakumarBalaganesh Muthiah
Mar 31, 2011·The Journal of Physical Chemistry. a·R SivaramakrishnanB Ruscic
May 24, 2011·The Journal of Physical Chemistry. a·Akira MatsugiAkira Miyoshi
Mar 8, 2012·The Journal of Physical Chemistry. a·R SivaramakrishnanS J Klippenstein

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