臺灣博碩士論文加值系統

Criegee intermediates are carbonyl oxides that play critical roles in the ozonolysis of alkenes in the atmosphere. So far, the infrared spectra of only the simplest Criegee intermediates CH2OO and CH3CHOO are reported. We report the transient infrared spectrum of the next member (CH3)2COO, produced from ultraviolet irradiation of a mixture of (CH3)2CI2 + O2 in a flow reactor and detected with a step-scan Fourier-transform spectrometer. The four observed bands provide definitive identification of (CH3)2COO. The observed vibrational wavenumbers and rotational contours agree with those predicted with quantum-chemical calculations. The rapid decay yields an estimate of the rate coefficient for self-reaction, ~1.610−10 cm3 molecule−1 s−1. The direct IR detection of (CH3)2COO should prove useful for field measurements and laboratory investigations of related Criegee mechanism.

Criegee intermediates are carbonyl oxides that play critical roles in the ozonolysis of alkenes in the atmosphere. So far, the infrared spectra of only the simplest Criegee intermediates CH2OO and CH3CHOO are reported. We report the transient infrared spectrum of the next member (CH3)2COO, produced from ultraviolet irradiation of a mixture of (CH3)2CI2 + O2 in a flow reactor and detected with a step-scan Fourier-transform spectrometer. The four observed bands provide definitive identification of (CH3)2COO. The observed vibrational wavenumbers and rotational contours agree with those predicted with quantum-chemical calculations. The rapid decay yields an estimate of the rate coefficient for self-reaction, ~1.610−10 cm3 molecule−1 s−1. The direct IR detection of (CH3)2COO should prove useful for field measurements and laboratory investigations of related Criegee mechanism.

Abstract i
Acknowledgement ii
List of Tables vi
List of Figures vii
Chapter 1. Introduction 1
Chapter 2 Experimental methods and techniques 9
2.1 Fourier-transform spectroscopy 9
2.1.1 Michelson interferometer 9
2.1.2 Fourier-transformation 11
2.1.3 Truncation function and Apodization function 12
2.1.4 Resolution 15
2.1.5 Phase correction 16
2.1.6 Configuration of an FTIR spectrometer 17
2.2 Step-scan FTIR spectrometer 18
2.2.1 Data acquisition of a step-scan FTIR spectrometer 19
2.2.2 Ac/dc-coupled detection 19
2.2.3 Aliasing and undersampling 21
2.3 Reference 33
Chapter 3 Experimental setup and procedure 35
3.1 Experimental setup 35
3.1.1 Laser system 35
3.1.2 Flow reactor and multipassing absorption cell 36
3.1.3 Spectrometer 37
3.1.4 Timing control of the ac-/ dc-coupled signal 38
3.2 Key factors in performing the experiment 40
3.2.1 Operations of preceding the experiment 40
3.2.2 Photolysis yield of precursors 40
3.2.3 Minimal detection limit of radicals 43
3.2.4 SNR (signal-to-noise ratio) of spectrum 44
3.2.5 Operation of the spectrometer (Bruker, Vertex 80v) 45
3.3 Experimental conditions 46
3.4 Parameters used in the OPUS program 47
3.4.1 Setup in a continuous-scan mode 47
3.4.2 Setup in a step-scan mode 48
3.4.3 Manual operation of Fourier transform (FT) 50
3.5 Reference 59
Chapter 4. Results and discussion 61
4.1 Reaction mechanisms in photolysis of (CH3)2CI2/N2/O2 61
4.1.1 Photo-irradiation of (CH3)2CI2/N2/O2 61
4.1.2 Self-reaction of (CH3)2COO 62
4.2 Computation results 62
4.3 Survey spectrum of (CH3)2CI2 /N2/O2 recorded at resolution 0.5 cm-1 63
4.4 Possible assignments of bands A1‒A4 64
4.4.1 Comparison of observed wavenumber with theoretical calculations 64
4.4.2 Simulations of rotational contours 65
4.4.3 Considerations of hot bands 66
4.4.4 Spectral reconstruction analysis (SRa) of band A1 67
4.4.5 Results of Spectral simulation 68
4.5 Estimate of the concentration of (CH3)2COO 70
4.6 Rapid decay kinetics of (CH3)2COO 72
4.7 Conclusion 72
4.8 Reference 93

1. W. H. Bunnelle, Chem. Rev. 91, 335 (1991).
2. S. Hatakeyama and H. Akimoto, Res. Chem. Intermed. 20, 503 (1994).
3. O. Horie and G. K. Moortgat, Acc. Chem. Res. 31, 387 (1998).
4. D. Johnson and G. Marston, Chem. Soc. Rev. 37, 699 (2008).
5. O. Horie and G. K. Moortgat, Acc. Chem. Res. 31, 387 (1998).
6. D. Johnson and G. Marston, Chem. Soc. Rev. 37, 699 (2008).
7. J. G. Calvert, R. Atkinson, J. A. Kerr, and S. Madroni, The Mechanisms Of Atmospheric Oxidation Of The Alkenes, Oxford University Press, New York, U. S. A. (2000).
8. O. Welz, J. D. Savee, D. L. Osborn, S. S. Vasu, C. J. Percival, D. E. Shallcross, and C. A. Taatjes, Science. 335, 204 (2012).
9. J. M. Beames, F. Liu, L. Lu, M. I. Lester, and J. Am. Chem. Soc. 134, 20045 (2012).
10. L. Sheps, J. Phys. Chem. Lett. 4, 4201 (2013).
11. W.-L. Ting, Y.-H. Chen, W. Chao, M. C. Smith, and J. J.-M. Lin, Phys. Chem. Chem. Phys. 16, 10438 (2014).
12. Y.-T. Su, Y.-H. Huang, H. A. Witek, and Y.-P. Lee, Science. 340, 174 (2013).
13. Y.-H. Huang, J. Li, H. Guo, Y.-P. Lee, J. Chem. Phys. 142, 214301 (2015).
14. M. Nakajima and Y. Endo, J. Chem. Phys. 139, 101103 (2013).
15. M. C. McCarthy, L. Cheng, K. N. Crabtree, O. Martinez, T. L. Nguyen, C. C. Womack, and J. F. Stanton, J. Phys. Chem. Lett. 4, 4133 (2013).
16. M. Nakajima, Q. Yue, J. Li, H. Guo, and Y. Endo, Chem. Phys. Lett. 621, 129 (2015).
17. A. M. Daly, B. J. Drouin, and S. Yu, J. Mol. Spectrosc. 297, 16 (2014).
18. Y.-T. Su, H.-Y. Lin, R. Putikam, H. Matsui, M. C. Lin, and Y.-P. Lee, Nat. Chem. 6, 477 (2014).
19. W.-L. Ting, C.-H. Chang, Y.-F. Lee, H. Matsui, Y.-P. Lee, and J. J.-M. Lin, J. Chem. Phys. 141, 104308 (2014).
20. A. Masaki, S. Tsunashima, and N. Washida, J. Phys. Chem. 99, 13126 (1995).
21. S. Enami, Y. Sakamoto, T. Yamanaka, S. Hashimoto, M. Kawasaki, K. Tonokura, and H. Tachikawa, Bull. Chem. Soc. Jpn. 81, 1250 (2008).
22. A. J. Eskola, D. Wojcik-Pastuszka, E. Ratajczak, and R. S. Timonen, Phys. Chem. Chem. Phys. 8, 1416 (2006).
23. D. Stone, M. Blitz, L. Daubney, T. Ingham, and P. Seakins, Phys. Chem. Chem. Phys. 15, 19119 (2013).
24. W.-L. Ting, C.-H. Chang, Y.-F. Lee, H. Matsui, Y.-P. Lee, and J. J.-M. Lin, J. Chem. Phys. 141, 104308 (2014).
25. C. A. Taatjes, O. Welz, A.J. Eskola, J.D. Savee, A.M. Scheer, D.E. Shallcross, B. Rotavera, E.P.F. Lee, J.M. Dyke, D. K. W. Mok, D.L. Osborn, and C. J. Percival, Science. 340, 177 (2013).
26. J. M. Beames, F. Liu, L. Lu, and M. I. Lester, J. Chem. Phys. 138, 244307 (2013).
27. M. C Smith, W.-L. Ting, C.-H. Chang, K. Takahashi, K. A. Boering, and J. J.-M. Lin, J. Chem. Phys. 141, 074302 (2014).
28. L. Sheps, A. M. Sculty, and K. Au, Phys. Chem. Chem. Phys. 16, 26701 (2014).
29. M. Nakajima and Y. Endo, J. Chem. Phys. 140, 011101 (2014).
30. M. Nakajima, Q. Yue, and Y. Endo, J. Mol. Spectrosc. 310, 109 (2015).
31. H.-Y. Lin, Y.-H. Huang, X. Wang, J. M. Bowman, Y. Nishimura, H. A. Witek, and Y.-P Lee, Nat. Comm. 6, 7012. (2015).
32. F. Liu, J. M. Beames, A. S. Petit, A. B. McCoy, and M. I. Lester, Science. 345, 1596 (2014).
33. S. E. Paulson and J. J. Orlando, Geophys. Res. Lett. 23, 3727 (1996).
34. F. Liu, J. M. Beames, A. M. Green, and M. I. Lester, J. Phys. Chem. A. 118, 2298 (2014).
35. H. L. Huang, W. Chao, J. J. Lin, Proc. Natl. Acad. Sci. USA, 112, 10857 (2015).
36. F. Liu, J. M. Beames, M. I. Lester, J. Chem. Phys. 141, 234312 (2014).
37. Y.-H. Huang and Y.-P. Lee, J. Chem. Phys. 141, 164302 (2014).
1. P. B. Fellgett, J. Pys. 7, 17 (1958)
2. P. Jacquinot, Rep. Progr. Phys. 23, 267 (1960).
3. J. Connes and P. Connes, J. Opt. Soc. Am. 56, 896 (1966).
4. W. R. Javan, Jr. Bennet, and D. R. Herriott, Phys. Rev. Lett. 6, 106 (1961).
A. A. Michelson, Philos. Mag. 31, 256 (1891).
5. A. Michelson, Light Waves and Their Uses, University of Chicago Press, Chicago, U.S.A. (1902).
6. D. A. Naylor and M. K. Tahic, J. Opt. Soc. Am. A, 24, 11 (2007).
7. L. Mertz, Transformations in Optics, Wiley, New York, U.S.A. (1965).
8. M. S. Braiman, P. L. Ahl, and K. J. Rothschild, Proc. Nat. Acad. Sci. U. S. A. 84, 5221 (1987).
9. D. E. Heard, R. A. Brownsword, D. G. Weston, and G. Hancock, Appl. Spectros. 47, 1438 (1993).
10. H. Sakai and R. E. Murphy, Appl. Opt., 17, 1342 (1978).
11. W. Barowy and H. Sakai, Infrared Phys. 24, 251 (1984).
12. L. Mertz, Infrared Phys. 7, 17 (1967).
13. H. Nyquist, AIEE Trans. 617, 644 (1928).
14. Y.-H. Huang, Ph.D. Dissertation, Detection of CH2BrOO, CH2OO, and CH2IOO with a step-scan time-resolved FTIR absorption spectrometer National Chiao Tung University (2015).
15. L.-W. Chen, Master Thesis, Simultaneous Infrared Detection of the ICH2OO Radical and Criegee Intermediate CH2OO: the Pressure Dependence of the Yield of CH2OO in the Reaction CH2I + O2, National Chiao Tung University (2016).
16. http://archive.lib.msu.edu/crcmath/math/math/a/a279.htm
17. Bruker's menu
1. Y.-H. Huang, Ph.D. Dissertation, Detection of CH2BrOO, CH2OO, and CH2IOO with a step-scan time-resolved FTIR absorption spectrometer, National Chiao Tung University (2015).
2. J. U. White, J. Opt. Soc. Am. 32, 285 (1942).
3. K.-H. Hsu, Master Thesis, National Chiao Tung University (2013).
4. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, Ö. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Gaussian 09, Revision 7.0, Wallingford CT, (2009).
5. PGopher, a Program for Simulating Rotational, Vibrational and Electronic Structure, version 8.0.282, C. M. Western, University of Bristol Research Data Repository; doi:10.5523/bris.huflggvpcuc1zvliqed497r2.
6. L.-W. Chen, Master Thesis, Simultaneous Infrared Detection of the ICH2OO Radical and Criegee Intermediate CH2OO: the Pressure Dependence of the Yield of CH2OO in the Reaction CH2I + O2, National Chiao Tung University (2016).
1. M. Kawasaki, S. J. Lee, and R. Bersohn, J. Chern. Phys. 63, 809 (1975).
2. S. L. Baughcum and S. R. Leone, J. Chem. Phys. 72, 6531 (1980).
3. C. Fotakis, M. Martin, and R. J. Donovan, J. Chem. Soc. Faraday Trans. 2 78, 1363 (1982).
4. U. Marvet and M. Dantus, Chem. Phys. Lett. 256, 57 (1996).
5. Y.-H. Huang, L.-W. Chen, and Y.-P. Lee, J. Chem. Phys. 6, 4610 (2015)
6. Y.-T. Su, H.-Y. Lin, R. Putikam, H. Matsui, M. C. Lin, Y.-P. Lee, Nat. Chem. 6, 477 (2014).
7. W.-L. Ting, C.-H. Chang, Y.-F. Lee, H. Matsui, Y.-P. Lee, and J. J.-M. Lin, J. Chem. Phys. 141, 104308 (2014).
8. M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman et al., Gaussian 09, revision A.02; Gaussian, Inc.: Wallingford, CT, 2009.
9. A. D. Becke, J. Chem. Phys. 98, 5648 (1993).
10. C. Lee, W. Yang, and R. G. Parr, Phys. Rev. B 37, 785 (1988).
11. T. H. Dunning, J. Chem. Phys. 90, 1007 (1989).
12. D. E. Woon and T. H. Dunning Jr., J. Chem. Phys. 98, 1358 (1993).
13. M. J. Wilhelm, J. M. Smith, and H.-L. Dai, J. Chem. Phys. 143, 124204 (2015).
14. Y.-Y, Wang, C.-Y Chung, and Y.-P. Lee, J. Chem. Phys. 145, 154303 (2016).
15. H.-Y. Lin, Y.-H. Huang, X. Wang, J.M. Bowman, Y. Nishimura, H.A.Witek, and Y.-P. Lee, Nat. Commun. 6, 7012 (2015).
16. Z. J. Buras, R. M.I. Elasmra, and W. H. Green, J. Phys. Chem. Lett. 5, 2224 (2014).
17. R. Chhantyal-pun, A. Davey, D. E. Shallcross, C. J. Percival, and A. J. OrrEwing, Phys. Chem. Chem. Phys. 17, 3617 (2015).