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

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: 29 May 2014
Fund Project:

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.
- Density functional theory calculation,
- Hydrate,
- Alkane,
- Stability,
- Raman spectrum
1. [1]
  
  (1) Sloan, E. D. Nature 2003, 426 (6964), 353. doi: 10.1038/nature02135
2. [2]
  (2) Englezos, P. Ind. Eng. Chem. Res. 1993, 32 (7), 1251. doi: 10.1021/ie00019a001
3. [3]
  (3) He, X. L.; Xia, N.; Liu, C. L.;Wang, J. T.; Meng, Q. G. J. Instrum. Anal. 2012, 31 (2), 206.
4. [4]
  (4) Prasad, P. S. R.; Sowjanya, Y.; Shiva, P. K. Vib. Spectrosc. 2009, 50 (2), 319. doi: 10.1016/j.vibspec.2009.02.003
5. [5]
  (5) Meng, Q. G.; Liu, C. L.; He, X. L.; Ye, Y. G.; Zhu, Y. H.; Xia, N. Geological Bulletin of China 2011, 30 (12), 1863. [孟庆国, 刘昌岭, 贺行良, 业渝光, 祝有海, 夏宁. 地质通报, 2011, 30 (12), 1863.]
6. [6]
  (6) Sum, A. K.; Burruss, R. C. J. Phys. Chem. B 1997, 101 (38), 7371. doi: 10.1021/jp970768e
7. [7]
  (7) Uchida, T.; Takeya, S.; Kamata, Y.; Ikeda, I. Y.; Nagao, J.; Ebinuma, T.; Narita, H.; Zatsepina, O.; Buffett, B. A. J. Phys. Chem. B 2002, 106 (48), 12426. doi: 10.1021/jp025884i
8. [8]
  (8) Subramanian, S.; Sloan, E. D. J. Phys. Chem. B 2002, 106 (17), 4348. doi: 10.1021/jp013644h
9. [9]
  (9) Tse, J. S. J. Supramol. Chem. 2002, 2, 429. doi: 10.1016/S1472-7862(03)00053-4
10. [10]
  (10) Ramya, K. R. J. Chem. Phys. 2012, 136 (17), 174305. doi: 10.1063/1.4707933
11. [11]
  (11) Yu, Y. Q.;Wang, Y. X.; Hu, N.Y.; Lin, K.; Zhou, X. G.; Liu, S. L. J. Raman Spectrosc. 2014, 45, 259. doi: 10.1002/jrs.4446
12. [12]
  (12) Cao, X. X.; Su, Y.; Liu, Y.; Zhao, J. J.; Liu, C. L. J. Chem. Phys. A 2014, 118, 252.
13. [13]
  (13) Chattaraj, P. K.; Bandaru, S.; Mondal, S. J. Phys. Chem. A 2011, 115 (2), 187. doi: 10.1021/jp109515a
14. [14]
  (14) Khan, A. J. Chem. Phys. 2002, 116 (15), 6628. doi: 10.1063/1.1462619
15. [15]
  (15) Lebsir, F.; Bouyacoub, A.; Bormann, D.; Krallafa, A. J. Mol. Struct. 2008, 864, 42. doi: 10.1016/j.theochem.2008.05.037
16. [16]
  (16) Koh, C. A.; Sum, A. K.; Sloan, E. D. J. Appl. Phys. 2009, 106 (6), 061101. doi: 10.1063/1.3216463
17. [17]
  (17) Gutt, C.; Asmussen, B.; Press,W.; Johnson, M. R.; Handa, Y. P.; Tse, J. S. J. Chem. Phys. 2000, 113 (11), 4713. doi: 10.1063/1.1288789
18. [18]
  (18) Rawn, C. J.; Rondinone, A. J.; Chakoumakos, B. C.; Circone, S. Stern, L. A.; Kirby, S. H.; Ishii, Y. Can. J. Phys. 2003, 81 (1-2), 431. doi: 10.1139/p03-022
19. [19]
  (19) Bernal, J. D.; Fowler, R. H. J. Chem. Phys. 1933, 1, 515. doi: 10.1063/1.1749327
20. [20]
  (20) Liu, Y.; Zhao, J. J.; Li, F. Y.; Chen, Z. F. J. Comput. Chem. 2013, 34 (2), 121. doi: 10.1002/jcc.23112
21. [21]
  (21) Grimme, S. J. Comput. Chem. 2006, 27 (15), 1787. doi: 10.1002/jcc.20495
22. [22]
  (22) Frisch, M. J.; Trucks, G.W.; Schlegel, H. B.; et al . Gaussian 09, Revision B.01; Gaussian Inc.:Wallingford, CT, 2011.
23. [23]
  (23) Fleischer, E. B.; Janda, K. C. J. Phys. Chem. A 2013, 117 (19), 4001. doi: 10.1021/jp311351j
24. [24]
  (24) Schrader, B. Raman/Infrared Atlas of Organic Compounds; Wiley: New York, 1989.
25. [25]
  (25) Pang, Y.; Zhang, Y. L.; Liao, Y. T.; Ma, S. Y. Journal of Beijing Normal University (Natural Science) 2005, 41 (5), 503. [庞岳, 张宇蕾, 廖玉婷, 马思渝. 北京师范大学学报(自然科学版), 2005, 41 (5), 503.]
26. [26]
  (26) Suzuki, M.; Tanaka, Y.; Sugahara, T.; Ohgaki, K. Chem. Eng. Sci. 2001, 56 (6), 2063. doi: 10.1016/S0009-2509(00)00489-9
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Stability and Raman Spectroscopy of Alkane Guest Molecules (CnHm, n≤6, m≤14) in 51262 and 51264 Water Cavities by Density Functional Theory Calculations

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通讯作者: 陈斌, bchen63@163.com

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