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
1. [1]
  Shitao Fu , Jianming Zhang , Cancan Cao , Zhihui Wang , Chaoran Qin , Jian Zhang , Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059
2. [2]
  Jiaxi Xu , Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049
3. [3]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
4. [4]
  Hailian Tang , Siyuan Chen , Qiaoyun Liu , Guoyi Bai , Botao Qiao , Fei Liu . Stabilized Rh/hydroxyapatite Catalyst for Furfuryl Alcohol Hydrogenation: Application of Oxidative Strong Metal-Support Interactions in Reducing Conditions. Acta Physico-Chimica Sinica, 2025, 41(4): 100036-. doi: 10.3866/PKU.WHXB202408004
5. [5]
  Baitong Wei , Jinxin Guo , Xigong Liu , Rongxiu Zhu , Lei Liu . Theoretical Study on the Structure, Stability of Hydrocarbon Free Radicals and Selectivity of Alkane Chlorination Reaction. University Chemistry, 2025, 40(3): 402-407. doi: 10.12461/PKU.DXHX202406003
6. [6]
  Bo YANG , Gongxuan LÜ , Jiantai MA . Corrosion inhibition of nickel-cobalt-phosphide in water by coating TiO₂ layer. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 365-384. doi: 10.11862/CJIC.20240063
7. [7]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
8. [8]
  Tianlong Zhang , Rongling Zhang , Hongsheng Tang , Yan Li , Hua Li . Online Monitoring and Mechanistic Analysis of 3,5-diamino-1,2,4-triazole (DAT) Synthesis via Raman Spectroscopy: A Recommendation for a Comprehensive Instrumental Analysis Experiment. University Chemistry, 2024, 39(6): 303-311. doi: 10.3866/PKU.DXHX202312006
9. [9]
  Qian Huang , Zhaowei Li , Jianing Zhao , Ao Yu . Quantum Chemical Calculations Reveal the Details Below the Experimental Phenomenon. University Chemistry, 2024, 39(3): 395-400. doi: 10.3866/PKU.DXHX202309018
10. [10]
  Jiaxun Wu , Mingde Li , Li Dang . The R eaction of Metal Selenium Complexes with Olefins as a Tutorial Case Study for Analyzing Molecular Orbital Interaction Modes. University Chemistry, 2025, 40(3): 108-115. doi: 10.12461/PKU.DXHX202405098
11. [11]
  Ronghao Zhao , Yifan Liang , Mengyao Shi , Rongxiu Zhu , Dongju Zhang . Investigation into the Mechanism and Migratory Aptitude of Typical Pinacol Rearrangement Reactions: A Research-Oriented Computational Chemistry Experiment. University Chemistry, 2024, 39(4): 305-313. doi: 10.3866/PKU.DXHX202309101
12. [12]
  Renqing Lü , Shutao Wang , Fang Wang , Guoping Shen . Computational Chemistry Aided Organic Chemistry Teaching: A Case of Comparison of Basicity and Stability of Diazine Isomers. University Chemistry, 2025, 40(3): 76-82. doi: 10.12461/PKU.DXHX202404119
13. [13]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166
14. [14]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
15. [15]
  Jingyi Chen , Fu Liu , Tiejun Zhu , Kui Cheng . Practice of Integrating Ideological and Political Education into Raman Spectroscopy Analysis Experiment Course. University Chemistry, 2024, 39(2): 140-146. doi: 10.3866/PKU.DXHX202310111
16. [16]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
17. [17]
  Zhaoyue Lü , Zhehao Chen , Yi Ni , Duanbin Luo , Xianfeng Hong . Multi-Level Teaching Design and Practice Exploration of Raman Spectroscopy Experiment. University Chemistry, 2024, 39(11): 304-312. doi: 10.12461/PKU.DXHX202402047
18. [18]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
19. [19]
  Jinghua Wang , Yanxin Yu , Yanbiao Ren , Yesheng Wang . Integration of Science and Education: Investigation of Tributyl Citrate Synthesis under the Promotion of Hydrate Molten Salts for Research and Innovation Training. University Chemistry, 2024, 39(11): 232-240. doi: 10.3866/PKU.DXHX202402057
20. [20]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191

Get Citation

PDF

XML

Metrics

PDF Downloads(566)
Abstract views(857)
HTML views(64)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

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

Metrics

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