Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers

doi:10.1021/acs.jpca.2c04724

	Metric-Based Assessment Method for MS-T Formalism with Small Subsets of Torsional Conformers
	Chi, Yicheng; Meng, Qinghui; He, Chengming; Zhang, Peng
发表期刊	JOURNAL OF PHYSICAL CHEMISTRY A ; 44
	2022-11-10
卷号	126 页码:8305-8314
ISSN	1089-5639
摘要	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
收录类别	SCI ; EI
语种	英语
WOS记录号	WOS:000878539300001
WOS研究方向	Chemistry, Physical ; Physics, Atomic, Molecular & Chemical
WOS类目	Chemistry ; Physics
项目资助者	National Natural Science Foundation of China [52176134] ; Hong Kong Polytechnic University (G-UAHP)
论文分区	二类
力学所作者排名	3
RpAuthor	Zhang, P
引用统计	被引频次：1[WOS] [WOS记录] [WOS相关记录]
文献类型	期刊论文
条目标识符	http://dspace.imech.ac.cn/handle/311007/91457
专题	高温气体动力学国家重点实验室
推荐引用方式 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.
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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