基于能量的分块方法研究生物柴油大分子脱氢反应
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- 英文论文题名：Study on Hydrogen Abstraction Reactions of Biodiesel Molecules using Generalized Energy-Based Fragmentation Method
- 论文作者：池亚微 ; 游小清 ; 张李东 ; 李伟
- 英文论文作者：Yawei Chi ; Xiaoqing You ; Lidong Zhang ; Wei Li ; Center for Combustion Energy ; Tsinghua University ; Key Laboratory for Thermal Science and Power Engineering of the Ministry of Education ; Tsinghua University ; National Synchrotron Radiation Laboratory ; University of Science and Technology of China ; School of Chemistry and Chemical Engineering ; Nanjing University
- 年：2016
- 作者机构：清华大学燃烧能源中心;清华大学热科学与动力工程教育部重点实验室;中国科学技术大学国家同步辐射实验室;南京大学化学化工学院;
- 论文关键词：生物柴油 ; 脱氢反应 ; GEBF方法 ; LSQC程序
- 会议召开时间：2016-07-01
- 会议录名称：中国化学会第30届学术年会摘要集-第四十六分会：燃烧化学
- 语种：中文
- 分类号：TE667
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-第四十六分会 ; 燃烧化学
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：168k
- 原文格式：D
- 会议级别：全国
摘要
生物柴油燃烧反应的理论研究得到了广泛的关注,然而庞大的计算量限制了传统的高精度量子化学计算方法在其中的应用。基于能量的分块方法(GEBF)是一种既能保证大分子能量计算准确度又能缩短计算时间的方法。它将大分子划分成小的碎片,再根据每个碎片临近的碎片结构将该碎片拼凑成完整的子体系分子,综合这些子体系分子的能量就可以得到整个分子的能量。这种方法的准确性和高效性已在很多大分子的结构优化、能量、频率等分子特性的计算中得到验证。本文采用基于GEBF方法的LSQC程序对酯类CnH2n+1COOCH3(n=4,5,6)的脱氢反应在QCISD(T)/CBS理论水平下进行了测试计算。计算结果表明,GEBF方法可以将计算时间缩减60%以上,同时得到与采用高精度量化方法直接计算大分子非常接近的结果,即便是对于有离域电子的自由基和过渡态,其能量计算的绝对误差也小于1 kcal/mol。
Combustion kinetics of biodiesels has attracted much attention theoretically, but the application of high-level quantum chemistry methods is very limited due to huge computational costs. Studies show that the generalized energy-based fragmentation(GEBF) method is very accurate and efficient for optimizing geometries and computing energies, vibration frequencies, etc. for many large systems. In this approach, a large molecule is divided into small fragments, and each fragment is capped by its neighboring fragments to form a subsystem. The total energy of the target molecule can be evaluated from the energies of all subsystems. In this work, we applied the low scaling quantum chemistry(LSQC) program that has implemented the GEBF method to study the hydrogen abstraction reactions of methyl esters at the QCISD(T)/CBS level. Results show that the computational time has been reduced by over 60% while the energy deviation is less than 1 kcal/mol for both radicals and transition states.
Combustion kinetics of biodiesels has attracted much attention theoretically, but the application of high-level quantum chemistry methods is very limited due to huge computational costs. Studies show that the generalized energy-based fragmentation(GEBF) method is very accurate and efficient for optimizing geometries and computing energies, vibration frequencies, etc. for many large systems. In this approach, a large molecule is divided into small fragments, and each fragment is capped by its neighboring fragments to form a subsystem. The total energy of the target molecule can be evaluated from the energies of all subsystems. In this work, we applied the low scaling quantum chemistry(LSQC) program that has implemented the GEBF method to study the hydrogen abstraction reactions of methyl esters at the QCISD(T)/CBS level. Results show that the computational time has been reduced by over 60% while the energy deviation is less than 1 kcal/mol for both radicals and transition states.
引文