Study on Anharmonic Effect of the Unimolecular Reaction of CH2(D2)FO

다국어 초록 (Multilingual Abstract)

Study on the unimolecular reaction for CH2FO and CD2FO is carried out. The structures, energy barriers and zero point energy of the three channels in the title unimolecular reactions are computed with the MP2/6- 311++G(3df, 3pd) method. RRKM theory is used to calculate the rate constants of canonical case at temperature range of 500–5000 K and microcanonical system at total energy of 19.05–71.68 kcal/mol. The results indicate that the anharmonic effect and isotope effect are very small for the three channels, and the anharmonic rate constants, around 109–1011 s−1, are close to the experimental prediction reasonably.

참고문헌 (Reference)

1 Rayez, J. C., 118 : 265-, 1987

2 Dibble, T. S., 485 : 67-71, 1999

3 LeBlanc, O. H., Jr., 33 : 598-, 1960

4 Forst, W., 71 : 339-, 1971

5 Forst, W., 53 : 3065-, 1970

6 Li, Q., 2 : 1-13, 2012

7 Li, Q., 90 : 186-, 2012

8 Gu, L. Z., 1-, 2011

9 Gu, Zh, L., 9 : 813-, 2010

10 Shao, Y., 501 : 134-, 2010

11 Yao, L., 113 : 14664-, 2009

12 Zachariah, M. R., 100 : 8737-, 1996

13 Tuazon, E. C., 17 : 179-, 1993

14 Wallington, T. J., 99 : 9437-, 1995

15 Krems, R., 214 : 1467-, 2000

16 Shen, D., 92 (92): 1297-, 1996

17 Hobza, P., 100 : 4253-, 2000

18 Tou, J. C., 49 : 4187-, 1968

19 Lin, S. H., 39 : 1577-, 1963

20 Lin, S. H., 43 : 2153-, 1964

21 McDowell, S. A. C., 770 : 119-, 2006

22 Bhuiyan, L. B., 78 : 5052-, 1983

23 Peslherbe, G. H., 105 : 7432-, 1996

24 Stein, S. E., 58 : 2438-, 1973

25 Beyer, T., 16 : 379-, 1973

26 Schlag, E. W., 37 : 168-, 1962

27 Hase, W. L., 31 : 659-, 1998

28 Song, K., 110 : 6198-, 1999

29 Bagratashvilli, V. N., 1 : 211-, 1983

30 Mitra, S. S., 27 : 1773-, 1994

31 Troe, J., 190 : 381-, 1995

32 Troe, J., 83 : 114-, 1979

33 Troe, J., 79 : 6017-, 1983

34 Romanini, D., 98 : 6437-, 1993

35 Forst, W., 53 : 3065-, 1970

36 Forst, W., 71 : 339-, 1971

37 Hoare, M. R., 52 : 113-, 1970

38 Eyring, H., 3 : 107-, 1935

39 Yao, L., 111 : 6722-, 2007

40 Yao, L., 22 : 3043-, 2008

41 Yao, L., 51 : 1146-, 2008

42 Yao, L., 470 : 210-, 2009

43 Shao, Y., 478 : 277-, 2009

44 Baer, T., "Unimolecular Reaction Dynamics: Theoryand Experiments" Oxford University Press 1996

45 Gilbert, R. G., "Theory of Unimolecular and Recombination Reactions" Blackwell 1990

46 Forst, W., "Theory of Unimolecular Reactions" Academic Press 1973

47 Forst, W., "Theory of Unimolecular Reactions" Academic Press 1973

48 Mills, I. M., "Theoretical Chemistry, The Chemical Society Vol. 1" Quantum Chemistry 110-, 1974

49 Huber, K. P., "IV Constants of Diatomic Molecules" Van Nostrand Reinhold Co 1979

50 Frisch, M. J., "GAUSS 03, revision C.02" Gaussian Inc 2004

51 Herzberg, G., "Electronic Spectra and Electronic Structure of Polyatomic Molecules" Van Nostrand Reinhold 1966

52 Qiong Luo, "Direct ab initio Dynamics Study of the Unimolecular Reaction of CH2FO" School of Science, Beijing Institute of Technology

53 Eyring, H., "Basic Chemical Kinetics" Wiley-Interscience Publication 1980