Utilization of generalized energy-based fragmentation method on the study of hydrogen abstraction reactions of large methyl esters
Utilization of generalized energy-based fragmentation method on the study of hydrogen abstraction reactions of large methyl esters
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利用广义能量裂解法研究大分子甲酯的夺氢反应
DOI：
10.1016/j.combustflame.2017.12.021
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发表时间：
2018-04
影响因子：
4.4
通讯作者：
Li Wei
中科院分区：
文献类型：
--
作者：
Chi Yawei;You Xiaoqing;Zhang Lidong;Li Wei
准确的反应能和势垒高度是建立各种燃料燃烧动力学模型的基础。然而，电子能量计算的计算成本使用高水平的实验室initiods的分子的大小显着增加。这个问题的解决方案是利用广义的基于能量的碎片化（GEBF）方法，因为已经发现它在利用各种量子化学方法计算许多大分子、簇和晶体的能量学和其他分子性质中有效地减少计算成本的缩放。本工作试图将GEBF方法应用于研究大分子甲酯的一种重要反应类型，即，氢原子的夺氢反应。在QCISD（T）/CBS// M06-2X/6-311 + + g（d，p）水平上，用量子化学方法和GEBF方法计算了CnH 2n +1COOCH 3（n= 4，5）+ H反应势能面上的驻点能量.计算结果表明，在QCISD（T）/cc-pVTZ水平上，GEBF方法与传统方法的无符号能量偏差小于0.1kcal/mol，计算时间大大缩短，最高可达90%。在量子化学计算的基础上，计算了CnH 2n +1COOCH 3（n= 4，5，8）与H原子的夺氢反应速率常数.
Accurate reaction energies and barrier heights are essential for the construction of reliable combustion kinetics models of various fuels. Nevertheless, the computational cost for electronic energy calculations using high-levelab initiomethods increases dramatically with the size of molecules. A solution to this problem is to utilize a generalized energy-based fragmentation (GEBF) approach, as it has been found to be effective in reducing the scaling of the computational cost in calculation of energetics and other molecular properties for many large molecules, clusters, and crystals with various quantum chemistry methods. This work attempts to apply this GEBF approach in the study of one important type of reactions of large methyl esters, i.e., the hydrogen abstraction reactions by hydrogen atoms. The energies of stationary points on the potential energy surfaces were examined using both conventional quantum chemistry methods and the GEBF method at the QCISD(T)/CBS// M06-2X/6-311 + + g(d,p) level for CnH2n+1COOCH3(n= 4, 5) + H reactions. The results show that the unsigned energy deviation of the GEBF method from the conventional method is less than 0.1 kcal/mol, while the computational time is greatly reduced, e.g. up to 90% at the QCISD(T)/cc-pVTZ level. Based on the quantum chemistry calculations, rate constants of the hydrogen abstraction reactions of CnH2n+1COOCH3(n= 4, 5, 8) by H atoms were computed.
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广义能量碎裂 CCSD(T)-F12a 方法及其在水团簇 (H2O)20 相对能量中的应用
影响因子：
5.5
作者：
Kedong Wang;Wei Li;Shuhua Li
通讯作者：
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影响因子：
4.4
作者：
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DOI：
10.1002/cphc.201200867
发表时间：
2013-01
期刊：
Chemphyschem : a European journal of chemical physics and physical chemistry
影响因子：
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作者：
Shugui Hua;Wei Li;Shuhua Li
通讯作者：
Shugui Hua;Wei Li;Shuhua Li
DOI：
10.1021/jp9098792
发表时间：
2010-04
期刊：
The journal of physical chemistry. A
影响因子：
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作者：
Sandeep Sharma;S. Raman;W. Green
通讯作者：
Sandeep Sharma;S. Raman;W. Green
DOI：
10.1063/1.4773011
发表时间：
2013-01
期刊：
The Journal of chemical physics
影响因子：
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作者：
Wei Li
通讯作者：
Wei Li