Accurate entropy calculation for large flexible hydrocarbons using a multi-structural 2-dimensional torsion method
Publication in refereed journal

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摘要Entropy is one of the key thermodynamic parameters in combustion kinetic modeling. Accurate entropy prediction needs to account for the conformational torsional anharmonicity, which could be solved by the state-of-the-art multi-structural torsion (MS-T) method. However, this method is computationally expensive or even not feasible for large flexible molecules. To address this issue, we proposed a multi-structural 2-dimensional torsion (MS-2DT) method that adopts minimally coupled torsions to reduce the computational cost. In this method, a series of 2-dimensional coupled torsion combinations were used to generate an initial conformer space with a size of CN2·9 (N is the number of torsions). The standard entropy (and the heat capacity) values of 18 C6–C8 alkanes with 5–7 torsions were computed at 200–2000 K. The MS-2DT calculation is in good agreement with the benchmark MS-T method: only a small deviation of −0.19 ± 0.15 cal mol−1 K−1 in standard entropy and −0.10 ± 0.21 cal mol−1 K−1 in heat capacity. Additionally, a further application of MS-2DT to n-decane with 9 torsions implies an improved accuracy in entropy (and heat capacity) prediction compared to other conventional simplified treatments. This method provides an affordable and accurate solution to treat the conformational torsional anharmonicity of large flexible alkanes.
出版社接受日期15.04.2019
著者Wu J., Ning H., Xu X., Ren W.
期刊名稱Physical Chemistry Chemical Physics
出版年份2019
卷號21
期次19
出版社Royal Society of Chemistry
頁次10003 - 10010
國際標準期刊號1463-9076
電子國際標準期刊號1463-9084
語言英式英語

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