The kinetics and mechanisms of H abstraction reaction between isoflurane and a CI atom have been investigated using DFT and G3（MP2） methods of theory. The geometrical structures of all species were optimized by the ...The kinetics and mechanisms of H abstraction reaction between isoflurane and a CI atom have been investigated using DFT and G3（MP2） methods of theory. The geometrical structures of all species were optimized by the wB97XD/6-311＋＋G＊＊ method. Intrinsic reaction coordinate （IRC） analysis has been carried out for the reaction channels. Thermochemistry data have been obtained by utilizing the high accurate model chemistry method G3（MP2） combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for reaction channels analysis. Two channels were obtained, which correspond to P（1） and P（2）. The rate constants for the two channels over a wide temperature range of 200-2000 K were also obtained. The results show that the barriers of P（1） and P（2） reaction channels are 50.36 and 50.34 kJ/mol, respectively, predicting that it exists two competitive channels. The calculated rate constant is in good agreement with the experiment value. Additionally, the results also show that the rate constants also increase from 1.85x10^-16 to 2.16x 10^12 cm3.moleculel.s-1 from 200 to 2000 K展开更多
基金financed by the Natural Science Foundation of Shaanxi Province(2014JM2046,2013JQ2027)the Special Natural Science Foundation of Science and Technology Bureau of Xi’an City Government(CXY1443WL03,CXY1352WL19 and CXY1352WL20)+1 种基金National Science Foundation of China(21303135)the Industrial research project of Science and Technology Department of Shaanxi Province(2013K09-25)
文摘The kinetics and mechanisms of H abstraction reaction between isoflurane and a CI atom have been investigated using DFT and G3（MP2） methods of theory. The geometrical structures of all species were optimized by the wB97XD/6-311＋＋G＊＊ method. Intrinsic reaction coordinate （IRC） analysis has been carried out for the reaction channels. Thermochemistry data have been obtained by utilizing the high accurate model chemistry method G3（MP2） combined with the standard statistical thermodynamic calculations. Gibbs free energies were used for reaction channels analysis. Two channels were obtained, which correspond to P（1） and P（2）. The rate constants for the two channels over a wide temperature range of 200-2000 K were also obtained. The results show that the barriers of P（1） and P（2） reaction channels are 50.36 and 50.34 kJ/mol, respectively, predicting that it exists two competitive channels. The calculated rate constant is in good agreement with the experiment value. Additionally, the results also show that the rate constants also increase from 1.85x10^-16 to 2.16x 10^12 cm3.moleculel.s-1 from 200 to 2000 K
