Citation: SONG Lei, YU Feng, WU Li-Xia, ZHOU Xiao-Guo, LIU Shi-Lin. Anionic Production Pathways Involved in the Reaction between OH^- and CH₂ClF[J]. Acta Physico-Chimica Sinica, ;2011, 27(04): 801-807. doi: 10.3866/PKU.WHXB20110409 shu

Anionic Production Pathways Involved in the Reaction between OH^- and CH₂ClF

SONG Lei ¹ ,
YU Feng ² ,
WU Li-Xia ¹ ,
ZHOU Xiao-Guo ^1, ,
LIU Shi-Lin ¹

1.
1. Hefei National Laboratory for Physical Sciences at the Microscale, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, P. R. China;
2. Department of Mathematics and Physics, Xi′an Technological University, Xi′an 710032, P. R. China

Received Date: 24 November 2010
Available Online: 2 March 2011
Fund Project: 国家自然科学基金(20603033, 10979042) (20603033, 10979042)国家重点基础研究发展规划(973) (2007CB815204)资助项目 (973) (2007CB815204)

The anionic production pathways involved in the reaction between hydroxide anion (OH^-) and chlorofluoromethane (CH₂ClF) were theoretically investigated. The optimized geometries of all the important species on the reaction potential energy surface were obtained at the B3LYP/6-31+G(d,p) and B3LYP/6-311++G(2d,p) levels. Consequently, harmonic vibrational frequencies and zero point energies (ZPEs) were calculated. Based on the relative energies of all the species that were calculated at the CCSD(T)/6-311+G(3df,3dp) level, the anionic production channels for the H⁺-abstraction and the bimolecular nucleophilic substitution (S_N2) reaction processes are elaborated upon. According to the calculated barrier heights for the production pathways, the H⁺-abstraction channel is dominant, which agrees very well with previous experimental conclusions. In addition, non-typical anionic products are suggested to form during the S_N2 reaction processes where the serious dynamic effect probably causes the S_N2 reaction process to produce F^-.
- Hydroxide anion,
- Chlorofluoromethane,
- Reaction mechanism,
- Proton transfer,
- Nucleophilic substitution (S_N2) reaction
1. [1]
  
  (1) Deckers, J.; van Tiggelen, A. Combust. Flame 1957, 1, 281.
2. [2]
  (2) Lee, J.; Grabowski, J. J. Chem. Rev. 1992, 92, 1611.
3. [3]
  (3) Fialkov, A. B. Prog. Energy Combust. Sci. 1997, 23, 399.
4. [4]
  (4) Grabowski, J. J.; Melly, S. J. Int. J. Mass Spectrom. 1987, 81, 147.
5. [5]
  (5) McFarland, M.; Albritton, D. L.; Fehsenfeld, F. C.; Ferguson, E. E.; Schmeltekopf, A. L. J. Chem. Phys. 1973, 59, 6610.
6. [6]
  (6) Beauchamp, J. L. Annu. Rev. Phys. Chem. 1971, 22, 527.
7. [7]
  (7) Futrell, J. H.; Miller, C. D. Rev. Sci. Instrum. 1966, 37, 1521.
8. [8]
  (8) Adams, N. G.; Smith, D. Int. J. Mass Spectrom. Ion Phys. 1976, 21, 349.
9. [9]
  (9) Bilotta, R. M.; Preuninger, F. N.; Farrar, J. M. J. Chem. Phys. 1980, 73, 1637.
10. [10]
  (10) Mayhew, C. A.; Peverall, R.; Timperley, C. M.; Watts, P. Int. J. Mass Spectrom. 2004, 233, 155.
11. [11]
  (11) Solomon, S. Rev. Geophys. 1999, 37, 275.
12. [12]
  (12) Rowland, F. S. Ambio 1990, 19, 281.
13. [13]
  (13) Molina, M. J.; Rowland, F. S. Nature 1974, 249, 810.
14. [14]
  (14) Bhatnagar, A.; Carr, R. W. Chem. Phys. Lett. 1996, 258, 651.
15. [15]
  (15) Blanco, S.; Lesarri, A.; López, J. C.; Alonso, J. L.; Guarnieri, A. J. Mol. Spectrosc. 1995, 174, 397.
16. [16]
  (16) http://en.wikipedia.org/wiki/Montreal_Protocol (accessed May 4, 2010).
17. [17]
  (17) Howle, C. R.; Mayhew, C. A.; Tuckett, R. P. J. Phys. Chem. A 2005, 109, 3626.
18. [18]
  (18) Peverall, R.; Kennedy, R. A.; Mayhew, C. A.; Watts, P. Int. J. Mass Spectrom. 1997, 171, 51.
19. [19]
  (19) Chiorboli, C.; Piazza, R.; Tosato, M. L.; Carassiti, V. Coord. Chem. Rev. 1993, 125, 241.
20. [20]
  (20) Bottoni, A.; Poggi, G.; Emmi, S. S. J. Mol. Struct. -Theochem 1993, 279, 299.
21. [21]
  (21) Tanner, S. D.; Mackay, G. I.; Bohme, D. K. Can. J. Chem. 1981, 59, 1615.
22. [22]
  (22) Yang, X.; Zhang, X.; Castleman, A. W. J. Phys. Chem. 1991, 95, 8520.
23. [23]
  (23) Yang, X.; Castleman, A. W. J. Am. Chem. Soc. 1991, 113, 6766.
24. [24]
  (24) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; et al. Gaussian 03, Revision C.02, D.01, E.01; Gaussian Inc.: Pittsburgh, PA, 2003.
25. [25]
  (25) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
26. [26]
  (26) Becke, A. D. J. Chem. Phys. 1993, 98, 1372.
27. [27]
  (27) Merrick, J. P.; Moran, D.; Radom, L. J. Phys. Chem. A 2007, 111, 11683.
28. [28]
  (28) nzalez, C.; Schlegel, H. B. J. Phys. Chem. 1990, 94, 5523.
29. [29]
  (29) nzalez, C.; Schlegel, H. B. J. Chem. Phys. 1989, 90, 2154.
30. [30]
  (30) Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
31. [31]
  (31) Purvis, G. D.; Bartlett, R. J. J. Chem. Phys. 1982, 76, 1910.
32. [32]
  (32) Urban, M.; Noga, J.; Cole, S. J.; Bartlett, R. J. J. Chem. Phys. 1985, 83, 4041.
33. [33]
  (33) Scuseria, G. E.; Janssen, C. L.; Schaefer, H. F. J. Chem. Phys. 1988, 89, 7382.
34. [34]
  (34) Curtiss, L. A.; Redfern, P. C.; Raghavachari, K.; Rassolov, V.; Pople, J. A. J. Chem. Phys. 1999, 110, 4703.
35. [35]
  (35) Baboul, A. G.; Curtiss, L. A.; Redfern, P. C.; Raghavachari, K. J. Chem. Phys. 1999, 110, 7650.
36. [36]
  (36) Yu, F.; Zhao, Y. G.; Wang, Y.; Zhou, X. G.; Liu, S. L. Acta Chim. Sin. 2007, 65, 899.
37. [37]
  [于锋, 赵英国, 王勇, 周晓国, 刘世林. 化学学报, 2007, 65, 899.]
38. [38]
  (37) Wang, X. L.; Yu, F.; Xie, D.; Liu, S. L.; Zhou, X. G. Acta Chim. Sin. 2008, 66, 2499.
39. [39]
  [王新磊, 于锋, 谢丹, 刘世林, 周晓国. 化学学报, 2008, 66, 2499.]
40. [40]
  (38) Wu, L. X.; Yu, F.; Song, L.; Zhou, X. G.; Liu, S. L. J. Mol. Struct. -Theochem 2010, 958, 82.
41. [41]
  (39) Yu, F.; Wu, L. X.; Zhou, X. G.; Liu, S. L. Chin. J. Chem. Phys. 2010, 23, 643.
42. [42]
  [于锋，吴琍霞，周晓国，刘世林. 化学物理学报, 2010, 23, 643.]
43. [43]
  (40) Borisov, Y. A.; Arcia, E. E.; Mielke, S. L.; Garrett, B. C.; Dunning, T. H. J. Phys. Chem. A 2001, 105, 7724.
44. [44]
  (41) Lee, E. P. F.; Dyke, J. M.; Mayhew, C. A. J. Phys. Chem. A 1998, 102, 8349.
45. [45]
  (42) Yu, F.; Wu, L. X.; Song, L.; Zhou, X. G.; Liu, S. L. J. Mol. Struct. -Theochem 2010, 958, 41.
46. [46]
  (43) Yu, F.; Wu, L. X.; Liu, S. L.; Zhou, X. G. J. Mol. Struct. -Theochem 2010, 947, 1.
47. [47]
  (44) Wu, L. X.; Yu, F.; Liu, J.; Dai, J. H.; Zhou, X. G.; Liu, S. L. Acta Phys. -Chim. Sin. 2010, 26, 2331.
48. [48]
  [吴琍霞, 于锋, 刘静, 戴静华, 周晓国, 刘世林. 物理化学学报, 2010, 26, 2331.]
49. [49]
  (45) Sun, L.; Song, K.; Hase, W. L. Science 2002, 296, 875.
50. [50]
  (46) Hase, W. L. Science 1994, 266, 998.
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Anionic Production Pathways Involved in the Reaction between OH- and CH2ClF

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Anionic Production Pathways Involved in the Reaction between OH^- and CH₂ClF