Imaging nucleophilic substitution dynamics

Science
J MikoschR Wester

Abstract

Anion-molecule nucleophilic substitution (S(N)2) reactions are known for their rich reaction dynamics, caused by a complex potential energy surface with a submerged barrier and by weak coupling of the relevant rotational-vibrational quantum states. The dynamics of the S(N)2 reaction of Cl- + CH3I were uncovered in detail by using crossed molecular beam imaging. As a function of the collision energy, the transition from a complex-mediated reaction mechanism to direct backward scattering of the I- product was observed experimentally. Chemical dynamics calculations were performed that explain the observed energy transfer and reveal an indirect roundabout reaction mechanism involving CH3 rotation.

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Citations

Oct 31, 2012·Journal of the American Chemical Society·Miguel A F de SouzaRicardo L Longo
Jan 18, 2013·Journal of the American Chemical Society·Jochen MikoschRoland Wester
Oct 9, 2009·Journal of the American Chemical Society·Jingjing ZhengDonald G Truhlar
Oct 28, 2011·The Journal of Physical Chemistry. a·Stephen J KlippensteinLawrence B Harding
Apr 13, 2012·The Journal of Physical Chemistry. a·Benjamin P FingerhutRegina de Vivie-Riedle
Mar 29, 2013·The Journal of Physical Chemistry. a·R OttoR Wester
May 8, 2010·Physical Chemistry Chemical Physics : PCCP·Stuart J GreavesAndrew J Orr-Ewing
Aug 9, 2008·Proceedings of the National Academy of Sciences of the United States of America·Brianna R HeazlewoodJoel M Bowman
May 9, 2012·Proceedings of the National Academy of Sciences of the United States of America·Gábor Czakó, Joel M Bowman
Apr 6, 2013·The Journal of Chemical Physics·Linsen Pei, James M Farrar
Dec 17, 2009·The Journal of Chemical Physics·Carsten Hennig, Stefan Schmatz
Feb 22, 2014·Nature Chemistry·Alexander von ZastrowSebastiaan Y T van de Meerakker
Mar 17, 2011·The Journal of Chemical Physics·S TrippelR Wester
Jan 15, 2011·Science·Qian ChenSteve Granick
Oct 23, 2012·The Journal of Chemical Physics·Linsen Pei, James M Farrar
May 2, 2009·The Journal of Chemical Physics·Gregory S EzraStephen Wiggins
Jun 14, 2013·The Journal of Chemical Physics·Martin SteiRoland Wester
Jun 7, 2012·The Journal of Chemical Physics·Linsen Pei, James M Farrar
Apr 10, 2014·The Journal of Chemical Physics·Frédéric A L MauguièreStephen Wiggins
Jul 10, 2014·Physical Chemistry Chemical Physics : PCCP·Antonio BauzáAntonio Frontera
Jan 12, 2011·Annual Review of Physical Chemistry·Joel M Bowman, Benjamin C Shepler
Jun 4, 2014·The Journal of Physical Chemistry. a·M KowalewskiR de Vivie-Riedle
Jun 22, 2012·Nature Chemistry·Andrew J Orr-Ewing
Feb 9, 2016·Journal of Chemical Theory and Computation·David B LingerfeltXiaosong Li
Jan 23, 2016·The Journal of Physical Chemistry. a·Eduardo CarrascosaRoland Wester
Jan 28, 2016·Chemical Record : an Official Publication of the Chemical Society of Japan ... [et Al.]·Antonio BauzáAntonio Frontera
Jan 23, 2016·Nature Chemistry·Martin SteiRoland Wester
Aug 12, 2015·The Journal of Physical Chemistry Letters·Linsen PeiJames M Farrar
Oct 27, 2015·The Journal of Physical Chemistry Letters·Frédéric A L MauguièreStephen Wiggins

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