Electron transfer NO
2
+
+NO→N02+NO+ in aromatic nitration |
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Authors: | Xiangyuan Li Fucheng He |
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Institution: | (1) Sichuan Union University, Department of Applied Chemistry, 610065 Chengdu, China |
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Abstract: | A simple model for computing the electron transfer rate constant of a cross-reaction has been proposed in the framework of
semiclassical theory and employed to investigate the electron transfer system NO
2
+
/NO. The encounter complex of electron transfer NO
2
+
+NO→N02+NO+ has been optimized at the level of UHF/6-31G. In the construction of diabatic potential energy surfaces the linear coordinate
was used and the kinetic quantities, such as the activation energies and the electron transfer matrix elements, have been
obtained. For comparison, the related selfexchange reactlon systems NO
2
+
/NO2 and NO+/NO were kinetically investigated. The calculated activation energies for the electron transfer reactions of systems NO
2
+
/NO, NO
2
+
/NO2, and NO+/NO are 81.4, 128.8, and 39.8 kJ.mol-1, respectively. With the solvent effect taken into account, the contribution of solvent reorganization to the activation energy
has been estimated according to the geometric parameters of the transition states. The obtained rate constants show that the
activity of NO
2
+
as an oxidizing reagent in the aromatic nitration will be greatly decreased due to a high activation barrier contributed
mainly from the change of bond angle ONO. |
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Keywords: | diabatic potential energy surface electron transfer matrix element reorganization energy rate constant |
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