Reaction dynamics simulations of the identity S(N)2 reaction H(2)O + HOOH(2)(+)--> H(2)OOH(+)+ H(2)O. Requirements for reaction and competition with proton transfer

Physical Chemistry Chemical Physics : PCCP
Christian Adlhart, Einar Uggerud

Abstract

Despite the fact that the transition structure of the gas phase S(N)2 reaction H(2)O + HOOH(2)(+)--> HOOH(2)(+)+ H(2)O is well below the reactants in potential energy, the reaction has not yet been observed by experiment. Variational transition state RRKM theory reveals a strong preference for the competing proton transfer reaction H(2)O + HOOH(2)(+)--> H(3)O(+)+ HOOH due to entropy factors. Born-Oppenheimer reaction dynamics simulations confirm these results. However, by increasing the collision energy to around 7.5 eV the probability for nucleophilic substitution increases relative to proton transfer. These observations are explained by the presence of the key common intermediate HOO(H)[dot dot dot]H-OH(2)(+) which leads to effective proton transfer, but can be avoided with increasing collision energy. However, the S(N)2 probability remains below 0.2 since successful passage through the TS requires optimum initial orientation of the reactants, excitation of the relative translational motion and good phase correlation between the O-O vibration and the motion of the incoming water.

References

May 4, 2002·Science·Lipeng SunWilliam L Hase
Sep 13, 2003·Organic & Biomolecular Chemistry·Jon K LaerdahlEinar Uggerud
Nov 13, 2004·Chemistry : a European Journal·Christian AdlhartEinar Uggerud

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Citations

Apr 2, 2014·ChemistryOpen·Lando P WoltersF Matthias Bickelhaupt
Nov 6, 2014·Physical Chemistry Chemical Physics : PCCP·Yaicel G ProenzaRicardo L Longo
May 17, 2011·Physical Chemistry Chemical Physics : PCCP·Hiroto Tachikawa
Oct 22, 2010·The Journal of Physical Chemistry. a·Thiago C Correra, José M Riveros

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