A simple model based on the statistics of individual atoms [Europhys. Lett. 94 40002 （2011）] or molecules [Chin. Phys. Lett. 29 080504 （2012）] was used to predict chemical reaction rates without empirical paramete...A simple model based on the statistics of individual atoms [Europhys. Lett. 94 40002 （2011）] or molecules [Chin. Phys. Lett. 29 080504 （2012）] was used to predict chemical reaction rates without empirical parameters, and its physical basis was further investigated both theoretically and via MD simulations. The model was successfully applied to some reactions of extensive experimental data, showing that the model is significantly better than the conventional transition state theory. It is worth noting that the prediction of the model on ab initio level is much easier than the transition state theory or unimolecular RRKM theory.展开更多
The mechanism of the reaction of N β dydroxyethylethylenediamine (HEDA) on copper under catalysis for the synthesis of piperazine was studied.The structures of reaction mixtures were identified by GC MS.The prelimina...The mechanism of the reaction of N β dydroxyethylethylenediamine (HEDA) on copper under catalysis for the synthesis of piperazine was studied.The structures of reaction mixtures were identified by GC MS.The preliminary study demonstrats that the above reaction is an intermolecular catalytic amination of alcohol and was proved to proceed through dehydrogenation and hydrogenation.Under the reaction conditions HEDA may undertake the bimolecular disproportionation reaction.Furthermore,the similar nucleophilic substitution reactions between starting material and products,between products and products,possibly occur to give the corresponding byproducts.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant No.11274073)the Leading Academic Discipline Project of Shanghai,China(Grant No.B107)
文摘A simple model based on the statistics of individual atoms [Europhys. Lett. 94 40002 （2011）] or molecules [Chin. Phys. Lett. 29 080504 （2012）] was used to predict chemical reaction rates without empirical parameters, and its physical basis was further investigated both theoretically and via MD simulations. The model was successfully applied to some reactions of extensive experimental data, showing that the model is significantly better than the conventional transition state theory. It is worth noting that the prediction of the model on ab initio level is much easier than the transition state theory or unimolecular RRKM theory.
文摘The mechanism of the reaction of N β dydroxyethylethylenediamine (HEDA) on copper under catalysis for the synthesis of piperazine was studied.The structures of reaction mixtures were identified by GC MS.The preliminary study demonstrats that the above reaction is an intermolecular catalytic amination of alcohol and was proved to proceed through dehydrogenation and hydrogenation.Under the reaction conditions HEDA may undertake the bimolecular disproportionation reaction.Furthermore,the similar nucleophilic substitution reactions between starting material and products,between products and products,possibly occur to give the corresponding byproducts.
