A product branching ratio controlled by vibrational adiabaticity and variational effects: kinetics of the H + trans-N2H2 reactions

The Journal of Chemical Physics
Jingjing ZhengDonald G Truhlar

Abstract

The abstraction and addition reactions of H with trans-N(2)H(2) are studied by high-level ab initio methods and density functional theory. Rate constants were calculated for these two reactions by multistructural variational transition state theory with multidimensional tunneling and including torsional anharmonicity by the multistructural torsion method. Rate constants of the abstraction reaction show large variational effects, that is, the variational transition state yields a smaller rate constant than the conventional transition state; this results from the fact that the variational transition state has a higher zero-point vibrational energy than the conventional transition state. The addition reaction has a classical barrier height that is about 1 kcal∕mol lower than that of the abstraction reaction, but the addition rates are lower than the abstraction rates due to vibrational adiabaticity. The calculated branching ratio of abstraction to addition is 3.5 at 200 K and decreases to 1.2 at 1000 K and 1.06 at 1500 K.

References

Nov 10, 2006·Chemical Reviews·Antonio Fernandez-RamosDonald G Truhlar
Dec 7, 2007·The Journal of Physical Chemistry. a·Benjamin A EllingsonDonald G Truhlar
Dec 18, 2007·The Journal of Chemical Physics·Thomas B AdlerHans-Joachim Werner
Feb 12, 2009·The Journal of Chemical Physics·Gerald KniziaHans-Joachim Werner
Apr 21, 2009·The Journal of Physical Chemistry. a·Yan ZhaoDonald G Truhlar
May 27, 2010·Physical Chemistry Chemical Physics : PCCP·Jingjing Zheng, Donald G Truhlar
Jun 11, 2011·Science·Peter R SchreinerWesley D Allen
Aug 1, 2008·Journal of Chemical Theory and Computation·Oksana TishchenkoDonald G Truhlar

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Citations

Dec 11, 2013·The Journal of Chemical Physics·Rene Felipe Keidel SpadaFrancisco Bolivar Correto Machado
Sep 11, 2014·Journal of Molecular Modeling·Daniely V V CardosoFrancisco B C Machado
Nov 26, 2015·The Journal of Physical Chemistry. a·Rene Felipe Keidel SpadaFrancisco Bolivar Correto Machado
Jul 22, 2014·Angewandte Chemie·Sharmistha Karmakar, Ayan Datta
Sep 10, 2014·The Journal of Physical Chemistry. a·Rene F K SpadaFrancisco B C Machado
Aug 20, 2019·Journal of the American Chemical Society·Cláudio M NunesPeter R Schreiner

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