| Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers | |
| Chi, Yicheng; Meng, Qinghui; He, Chengming; Zhang, Peng | |
| Source Publication | JOURNAL OF PHYSICAL CHEMISTRY A
 ; 44
|
| 2022-11-10 | |
| Volume | 126Pages:8305-8314 |
| ISSN | 1089-5639 |
| Abstract | The multi-structural approximation with torsional anharmonicity (MS-T) method and its variants have been widely used for calculating conformational-rovibrational partition functions of large molecules. The present work aimed to propose a systematic method to assess and explain the performance of various variants of the MS-T method. First, we proposed the simplest variant MS-T(2NN) (two nearest neighborhood torsions are coupled) and systematically validated it for large alkanes n-CnH2n+2 (n = 6-10) and their transition states of hydrogen abstraction reactions. Second, we proposed a metric-based method to explain the underlying reason for the good performance of MS-T(2NN)-it includes the torsional conformers that have dominant contributions to the partition function calculations. These conformers are closer to the lowest-energy conformer in the space of dihedral and energy metrics. Third, the same observation and explanation apply to the other two variants, MS-2DT (any two torsions are coupled) and MS-3DT (any three torsional are coupled), which contain increasingly more torsional conformers than MS-T(2NN) but are subsets of the complete set of torsional conformers considered by the MS-T method. Overall, the present method provides a mathematically rigorous and computationally effective diagnosis tool to assess various MS-T methods dealing with the torsional anharmonicity of large molecules in the partition function calculation. |
| DOI | 10.1021/acs.jpca.2c04724 |
| Indexed By | SCI ; EI |
| Language | 英语 |
| WOS ID | WOS:000878539300001 |
| WOS Research Area | Chemistry, Physical ; Physics, Atomic, Molecular & Chemical |
| WOS Subject | Chemistry ; Physics |
| Funding Organization | National Natural Science Foundation of China [52176134] ; Hong Kong Polytechnic University (G-UAHP) |
| Classification | 二类 |
| Ranking | 3 |
| Contributor | Zhang, P |
| Citation statistics | |
| Document Type | 期刊论文 |
| Identifier | http://dspace.imech.ac.cn/handle/311007/91457 |
| Collection | 高温气体动力学国家重点实验室 |
| Recommended Citation GB/T 7714 | Chi, Yicheng,Meng, Qinghui,He, Chengming,et al. Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers[J]. JOURNAL OF PHYSICAL CHEMISTRY A, 44,2022,126:8305-8314.Rp_Au:Zhang, P |
| APA | Chi, Yicheng,Meng, Qinghui,He, Chengming,&Zhang, Peng.(2022).Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers.JOURNAL OF PHYSICAL CHEMISTRY A,126,8305-8314. |
| MLA | Chi, Yicheng,et al."Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers".JOURNAL OF PHYSICAL CHEMISTRY A 126(2022):8305-8314. |
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| Jp2022FA073.pdf（5427KB） | 期刊论文 | 出版稿 | 开放获取 | CC BY-NC-SA | View Download | |
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