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研究生:蘇夏琳
研究生(外文):Charlene Su
論文名稱:超快時間解析激態分子內質子轉移反應
論文名稱(外文):Ultrafast Time-resolved Spectroscopic Studies of Gas-Phase Excited-State Intramolecular Proton Transfer Reactions
指導教授:鄭博元 
指導教授(外文):Prof. Po-Yuan Cheng
學位類別:碩士
校院名稱:國立清華大學
系所名稱:化學系
學門:自然科學學門
學類:化學學類
論文種類:學術論文
論文出版年:2002
畢業學年度:90
語文別:英文
論文頁數:122
中文關鍵詞:超快時間解析激態分子內質子轉移
外文關鍵詞:UltrafastTime-resolvedExcited-State Intramolecular Proton Transfero-hydroxyacetophenonemultiphoton ionization
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The excited-state dynamics of o-hydroxyacetophenone (OHAP) and its related molecules have been studied in the gas phase using femtosecond time-resolved multiphoton ionization spectroscopy. Following femtosecond excitation to their S1 state, the OHAPs were found to exhibit a biexponential decay behavior coupled with a rapidly damped low-frequency oscillation. The hydroxy deuterated OHAP showed a significant isotope effect, indicating that the oscillation is related to the H-atom motion. The combination of experimental and theoretical results suggested that, although the initial motion in the excited-state intramolecular proton transfer occurs in less than 100 fs, a low-frequency vibration motion involving both O…O and O-H stretches may allow the system to oscillation between the two tautomeric forms.

Abstract ……………………………………………………………………i
Acknowledgements …………………………………………………………ii
Contents ……………………………………………………………………iii
List of figures……………………………………………………………v
List of tables ……………………………………………………………ix
Chapter 1: Introduction …………………………………………………1
1.1 Excited state intramolecular proton transfer (ESIPT) …2
1.2 A brief review on o-hydroxybenzaldehyde (OHBA) …………4
1.3 A brief review on o-hydroxyacetophenone (OHAP) …………9
1.4 This work …………………………………………………………12
Chapter 2: Experimental…………………………………………………30
2.1 Methodology ………………………………………………………30
2.2 Experimental setup………………………………………………33
2.2.1 Ultrafast laser system ………………………………33
2.2.2 Optics layout……………………………………………36
2.2.3 Flow cell…………………………………………………38
2.2.4 Molecular beam apparatus ……………………………40
2.2.5 Time-of-flight mass spectrometer (TOF-MS)………43
2.2.6 Data acquisition ………………………………………45
2.3 Cross correlation ………………………………………………47
2.4 Chemicals …………………………………………………………48
2.5 UV absorption spectra …………………………………………50
Chapter 3: Experimental Results and Analyses ……………………67
3.1 OHAP transients and data analyses …………………………67
3.2 Laser irradiance dependence …………………………………70
3.3 Pump-laser wavelength dependence of the transients……72
3.4 Substitution position effect: OHAP and MHAP ……………74
3.5 Alkyl-substitution position effect: OHAP and MHAP ……75
3.6 Isotope effect: OHAP and ODAP ………………………………77
Chapter 4: Theoretical Calculation and Discussion………………94
4.1 Reaction mechanism………………………………………………94
4.2 Ab initio calculations…………………………………………96
4.2.1 Vertical excitation and ionization energy………96
4.2.2 Potential energy profile along the S1(p,p*) CIS-
MEP…………………………………………………………99
4.2.3 Potential energy surface of S1(p,p*) state……102
4.3 Low-frequency vibrational motion …………………………103
4.4 The origin of transient oscillation………………………104
4.5 Dynamic of proton transfer reaction………………………105
Chapter 5: Conclusion …………………………………………………118
Chapter 6: Reference……………………………………………………120

1. J. L. Herek, S. Pedersen, L. Bañares, and A. H. Zewail, J. Chem. Phys., 97, 9046 (1992)
2. P. T. Chou, D. McMorrow, T. J. Aartsma, M.J. Kasha, J. Phys. Chem., 88, 4596 (1984)
3. A. Douhal, R. Sastre, Chem. Phys. Lett., 219, 91 (1994)
4. M.L. Martinez, W. C. Cooper, P. T. Chou, Chem. Phys. Lett., 193, 151 (1992)
5. D. L. Williams, J. Heller, J. Phys. Chem., 74, 4473 (1970)
6. R. M. Tarkka, X. Zhang, S. A. Jenekhe, J. Am. Chem. Soc., 118, 9438 (1996)
7. A. Sytnik, M. Kasha, Proc. Nat. Acad. Sci. U.S.A. 91, 8627 (1994)
8. A. Sytnik, J. C. Del Valle, J. Phys. Chem., 99, 13028 (1995)
9. A. Weller, Z. Elecktrochem., 60, 1144 (1956)
10. L. Helmbrook, J.E. Kenny, B. E. Kohler and G. W. Scott, J. Chem. Phys., 75, 5201 (1981); J. Phys. Chem., 87, 280 (1983)
11. A. Douhal, F. Lahmani, A. H. Zewail, Chem. Phys., 207, 477 (1996)
12. C. J. Seliskar, J. Mol. Spec., 53, 140 (1974)
13. J. Catalán, and A. U. Acuña, J. Phys. Chem., 86, 303 (1982)
14. S. Nagaoka, U. Nagashima, J. Phys. Chem., 92, 166 (1988)
15. S. Nagaoka, N. Hirota, M. Sumitani, and K. Yoshihara, J. Am. Chem. Soc., 105, 4220 (1983)
16. S. Nagaoka and U. Nagashima, Chem. Phys., 136, 153 (1989)
17. A. Douhal, F. Amat-Guerri and A. U. Acuña, J. Phys. Chem., 99,76 (1995)
18. J. Konijnenberg, A. H. Huizer and Cyril A. G. O. Varma, J. chem. Soc, Faraday Trans., 84, 363 (1988)
19. A. L. Sobolewski, and W. Domcke, Phys. Chem. Chem. Phys., 1, 3065 (1999)
20. S. Lochbrunner, T. Schultz, M. Schmitt, J. P. Shaffer, M. Z. Zgierski, and Albert Stolow, J. Chem. Phys., 114, 2519 (2001)
21. T. Nishiya, S. Yamauchi, N. Hirota, M. Baba, and . Hanazaki, J. Phys. Chem., 90, 5730 (1986)
22. M. V. Vener and S. Scheiner, J. Phys. Chem., 99, 642 (1995)
23. Graham R. Fleming, Chemical Applications of Ultrafast Spectroscopy, chapter 4, Oxford University Press (1986)
24. User’s manual of mode-locked Ti:sapphire laser (Tsunami), spectra-physics laser (1995)
25. User’s manual of multikilohertz pulsed Ti:sapphire Amplifier (Spitfire), spectra- physics laser
26. User’s manual of ultrafast kHz optical parametric oscillator (OPA), spectra- physics laser (1997)
27. L. Dunnoyer, Le Radium, 8, 142 (1911)
28. John H. Moore, Christopher C. Davis, Michael A. Coplan, Building Scientific Apparatus: A practical Guide to Design and Construction 2nd ed., 99-102, Addison-Wesley Publishing Company (1989)
29. W. C. Wiley, I. H. McLaren, Rev. Sci. Instrum., 26, 1150 (1955)
30. Wolfga Demtröder, Laser Spectroscopy: basic concepts and instrumentation 2nd ed., 624-630, Springer-Verlag Berlin Heidelberg (1996)
31. Shin-ichi Nagaoka, Yoshikazu Shinde, Kazuo Mukai, and Umpei Nagashima, J. Phys. Chem. A, 101, 3061 (1997)
32. NIST Chemistry Web, http://webbook.nist.gov/chemistry
33. A. L. Sobolewski and W. Domck, Chem. Phys., 184, 115 (1994)
34. Gaussian 98, Revision A.9, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski, J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, J. V. Ortiz, A. G. Baboul, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 1998.

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