烷烃客体分子(CnHm, n≤6, m≤14)在51262和51264水笼中的稳定性与拉曼光谱的密度泛函理论计算

引用本文: 曹潇潇, 苏艳, 赵纪军, 刘昌岭, 周潘旺. 烷烃客体分子(C_nH_m, n≤6, m≤14)在5¹²6²和5¹²6⁴水笼中的稳定性与拉曼光谱的密度泛函理论计算[J]. 物理化学学报, 2014, 30(8): 1437-1446. doi: 10.3866/PKU.WHXB201405292 shu

Citation: CAO Xiao-Xiao, SU Yan, ZHAO Ji-Jun, LIU Chang-Ling, ZHOU Pan-Wang. Stability and Raman Spectroscopy of Alkane Guest Molecules (C_nH_m, n≤6, m≤14) in 5¹²6² and 5¹²6⁴ Water Cavities by Density Functional Theory Calculations[J]. Acta Physico-Chimica Sinica, 2014, 30(8): 1437-1446. doi: 10.3866/PKU.WHXB201405292 shu

烷烃客体分子(C_nH_m, n≤6, m≤14)在5¹²6²和5¹²6⁴水笼中的稳定性与拉曼光谱的密度泛函理论计算

基金项目:
国家自然科学基金（11174045，11304030)

中央高校基本科研业务费专项资金（DUT₁4LK19）资助项目

摘要:

可燃冰矿藏中气体成分非常复杂，通过谱学分析对水合物样品成分进行指认具有重要意义.基于B97-D/6-311++G（2d，2p）的密度泛函理论（DFT）计算，我们系统地探索了构成水合物的两种标准水笼（5¹²6²和5¹²6⁴）包络十八种不同烷烃客体分子的稳定性. 从计算结果可以看出，除了3-甲基戊烷和2，3-二甲基丁烷两个烷烃客体分子，其它16个烷烃客体分子都可以被容纳在5¹²6²笼中；但是与5¹²6²笼不同，十八种烷烃客体分子都可以被容纳在尺寸较大的5¹²6⁴笼中. 同时，我们也模拟了五种直链烷烃和四种环状烷烃在5¹²6²和5¹²6⁴笼中相应的谱学特征，从拉曼谱图上可以看出，随着碳原子数量的增多，直链烷烃客体分子C―H键伸缩振动区的多数拉曼谱带向高波数移动，而环状烷烃客体分子C―H键伸缩振动区的拉曼谱带则向低波数移动. 这些结果为实验上通过拉曼谱测量指认水合物矿藏的成分提供理论参考.

关键词:

English

Stability and Raman Spectroscopy of Alkane Guest Molecules (C_nH_m, n≤6, m≤14) in 5¹²6² and 5¹²6⁴ Water Cavities by Density Functional Theory Calculations

1.
1. Laboratory of Materials Modification by Laser, Ion and Electron Beams of the Ministry of Education, Dalian University of Technology, Dalian 116024, Liaoning Province, P. R. China;
2. Key Laboratory of Marine Hydrocarbon Resources and Environmental Geology, Ministry of Land and Resources, Qingdao 266071, Shandong Province, P. R. China;
3. Qingdao Institute of Marine Geology, Qingdao 266071, Shandong Province, P. R. China;
4. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116024, Liaoning Province, P. R. China
Received Date: 21 April 2014
Available Online: 18 July 2014
Fund Project:
国家自然科学基金（11174045，11304030)

中央高校基本科研业务费专项资金（DUT₁4LK19）资助项目

Abstract:

The gas composition in natural gas hydrate deposits is complex, and therefore the use of spectroscopic analysis to elucidate the chemical composition is of great significance. Using density functional theory (DFT) calculations at the B97-D/6-311++G(2d, 2p) level, we systematically explored the stability of 18 alkane guest molecules in two standard water cavities (5¹²6² and 5¹²6⁴). The results indicated that most alkane guest molecules can be stored in the 5¹²6² cage, with the exception of 3-methylpentane and 2,3-dimethylbutane, while all 18 alkanes can be encapsulated in the 5¹²6⁴ cage. The Raman spectroscopic characteristics of five straight-chain and four cyclic alkane guest molecules in the 5¹²6² and 5¹²6⁴ cages were also simulated. The majority of the Raman bands of the straight-chain alkanes in the C―H stretching region were found to move to higher wavenumbers as the number of carbon atoms increased, while most bands of the cyclic molecules in this region transitioned to lower wavenumbers. These theoretical results should prove helpful with regard to identifying hydrate deposits from experimental Raman spectroscopic data.

Key words:

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烷烃客体分子(C_nH_m, n≤6, m≤14)在5¹²6²和5¹²6⁴水笼中的稳定性与拉曼光谱的密度泛函理论计算

English

Stability and Raman Spectroscopy of Alkane Guest Molecules (C_nH_m, n≤6, m≤14) in 5¹²6² and 5¹²6⁴ Water Cavities by Density Functional Theory Calculations

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