学科主题:  物理化学

题名:  Thermal Rate Constants and ReaxFF MD simulation of the Pyrolysis of nHeptane 
作者:  Ding JX(丁俊霞)
; Zhang L(张亮)
; Han KL(韩克利)

会议文集:  International Conference on Theoretical and High Performance Computational Chemistry 2011

会议名称:  International Conference on Theoretical and High Performance Computational Chemistry 2011

会议日期:  2011811

出版日期:  2011

会议地点:  西安

通讯作者:  韩克利

出版者:  待补充

出版地:  待补充

合作性质:  墙报

部门归属:  1101

主办者:  中国科学院超级计算中心

摘要:  The pyrolysis mechanism and kinetics of nHeptane are investigated by using statisticaltheoretical methodology and reactive molecular dynamics (ReaxFF MD) simulation. Firstly, we studied the temperature and pressure dependence rate constants of pyrolysis of nHeptane in detail. The pyrolysis mechanism includes the important Preaction, βscission reaction and Hatom abstraction reaction, consisting of 22 species, 28 reactions and 25 transition states. The energy barrier and geometrical parameters of transition states have been calculated at a high level of CCSD (T)/6311G (d, p)//B3LYP/6311G (d, p). The temperaturedependent rate constants for individual reaction have been obtained in the temperature range of 2003000 K using variational transition state theory and Rice–Ramsperger–Kassel–Marcus theory. The pressure dependence rate constants have been treated by onedimensional master equation calculations at different pressure as well as highpressure limit. Threeparameter fittings of the calculated rate constants are given at several different pressures. Secondly, we carried out molecular dynamics (MD) simulation employing the ReaxFF reactive force field. We found the initiation mechanism of decomposition of nHeptane involve the cleavage of CC bond, resulting in the formation of smaller radicals. The free radical chain mechanism of pyrolysis of hydrocarbons can be proved from the MD result. ReaxFF MD leads to good agreement with experiment for the product distribution as a function of conversion of reactant. Moreover, based on the firstorder kinetic analysis of nHeptane, we calculate an activation energy of 51.19 kcal/mol, which is consisted with the experimental result. Besides, temperaturedependent MD simulations give the detailed pyrolysis distributions of nHeptane at high temperature and the temperature influences on the kinetics mechanism of pyrolysis of nHeptane. 
英文摘要:  The pyrolysis mechanism and kinetics of nHeptane are investigated by using statisticaltheoretical methodology and reactive molecular dynamics (ReaxFF MD) simulation. Firstly, we studied the temperature and pressure dependence rate constants of pyrolysis of nHeptane in detail. The pyrolysis mechanism includes the important Preaction, βscission reaction and Hatom abstraction reaction, consisting of 22 species, 28 reactions and 25 transition states. The energy barrier and geometrical parameters of transition states have been calculated at a high level of CCSD (T)/6311G (d, p)//B3LYP/6311G (d, p). The temperaturedependent rate constants for individual reaction have been obtained in the temperature range of 2003000 K using variational transition state theory and Rice–Ramsperger–Kassel–Marcus theory. The pressure dependence rate constants have been treated by onedimensional master equation calculations at different pressure as well as highpressure limit. Threeparameter fittings of the calculated rate constants are given at several different pressures. Secondly, we carried out molecular dynamics (MD) simulation employing the ReaxFF reactive force field. We found the initiation mechanism of decomposition of nHeptane involve the cleavage of CC bond, resulting in the formation of smaller radicals. The free radical chain mechanism of pyrolysis of hydrocarbons can be proved from the MD result. ReaxFF MD leads to good agreement with experiment for the product distribution as a function of conversion of reactant. Moreover, based on the firstorder kinetic analysis of nHeptane, we calculate an activation energy of 51.19 kcal/mol, which is consisted with the experimental result. Besides, temperaturedependent MD simulations give the detailed pyrolysis distributions of nHeptane at high temperature and the temperature influences on the kinetics mechanism of pyrolysis of nHeptane. 
语种:  英语

内容类型:  会议论文

URI标识:  http://casir.dicp.ac.cn/handle/321008/115982

Appears in Collections:  中国科学院大连化学物理研究所_会议论文

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Recommended Citation: 
Ding JX,Zhang L,Han KL. Thermal Rate Constants and ReaxFF MD simulation of the Pyrolysis of nHeptane[C]. 见:International Conference on Theoretical and High Performance Computational Chemistry 2011. 西安. 2011811.


