Femtosecond mid-infrared spectroscopy of elementary photoinduced reactions [Elektronische Ressource] / von Matteo Rini

Sujets

• Physik

Informations

• Publié par: humboldt-universitat_zu_berlin
• Publié le: 01 janvier 2003
• Nombre de lectures: 102
• Langue: Deutsch
• Poids de l'ouvrage: 10 Mo

Extrait

Femtosecond Mid-Infrared Spectroscopy of
Elementary Photoinduced Reactions
DISSERTATION
zur Erlangung des akademischen Grades
doctor rerum naturalium
(dr. rer. nat.)
im Fach Physik
eingereicht an der
Mathematisch-Naturwissenschaftlichen Fakultät I
Humboldt-Universität zu Berlin
von
Herr Dipl.-Ing. Matteo Rini
Präsident der Humboldt-Universität zu Berlin:
Prof. Dr. J. Mlynek
Dekan der Mathematisch-Naturwissenschaftlichen Fakultät I:
Prof. Dr. M. Linscheid
Gutachter:
1. Prof. Dr. Thomas Elsaesser
2. Prof. Dr. Nikolaus Schwentner
3. Prof. Dr. Jürgen P. Rabe
eingereicht am: 17. Juli 2003
Tag der mündlichen Prüfung: 12. Dezember 2003Hiermiterkläreich,dieDissertationselbstständigundohneunerlaubteHilfeange-
fertigt zu haben.
IchhabemichanderwärtsnichtumeinenDoktorgradbeworbenundbesitzeeinen
entsprechenden Doktorgrad nicht.
IcherkläredieKenntnisnahmederdemVerfahrenzugrundeliegendenPromotion-
sordnung der Mathematisch-Naturwissenschaftlichen Fakultät I der Humboldt-
Universität zu Berlin.
Berlin, den 15. Juli 2003 Matteo Rini
iiiVeröffentlichungen im Zusammenhang mit dieser Arbeit
Publications in conjunction with this thesis
[1] M. Rini, B. Z. Magnes, E. Pines, and E. T. J. Nibbering, “Real-time observa-
tion of bimodal proton transfer in acid-base pairs in water,” Science (2003),
in press.
[2] A. K. Holm, M. Rini, E. T. J. Nibbering, and H. Fidder, “Femtosecond
UV/mid-IR study of photochromism of the spiropyran 1’,3’-dihydro-1’,3’,3’-
trimethyl-6-nitrospiro[2H-1-benzopyran-2,2’-(2H)-indole] in solution,” Chem.
Phys. Lett. 376, 214–219 (2003).
[3] M. Rini, J. Dreyer, E. T. J. Nibbering, and T. Elsaesser, “Ultrafast vibra-
tional relaxation processes induced by intramolecular excited state hydrogen
transfer,” Chem. Phys. Lett. 374, 13–19 (2003).
[4] M. Rini, A. K. Holm, E. T. J. Nibbering, and H. Fidder, “Ultrafast UV-mid-
IR investigation of the ring opening reaction of a photochromic spiropyran,”
J. Am. Chem. Soc. 125, 3028–3034 (2003).
[5] M. Rini, A. Kummrow, J. Dreyer, E. T. J. Nibbering, and T. Elsaesser, “Ul-
trafast site-specific mid-infrared spectroscopy of excited-state intramolecular
proton transfer,” In Ultrafast Phenomena XIII, R. D. Miller, M. M. Murnane,
N.F.Scherer,andA.M.Weiner,eds.,SpringerSer.Chem.Phys.71, 465–467
(Springer, Berlin, 2003).
[6] M. Rini, A. Kummrow, J. Dreyer, E. T. J. Nibbering, and T. Elsaesser,
“Femtosecondmid-infraredspectroscopyofcondensedphasehydrogen-bonded
systems as a probe of structural dynamics,” Faraday Discuss. 122, 27–40
(2002).
Andere Veröffentlichungen/Other publications:
[1] R. Grunwald, V. Kebbel, U. Griebner, U. Neumann, A. Kummrow, M. Rini,
E. T. J. Nibbering, M. Piché, G. Rousseau, and M. Fortin, “Generation and
characterization of spatially and temporally localized few-cycle optical wave
packets,” Phys. Rev. A 67, 063820 (2003).
[2] R. Grunwald et al., “Generation of ultrashort-pulse nondiffracting beams and
X-waves with thin-film axicons,” In Ultrafast Phenomena XIII, R. D. Miller,
M. M. Murnane, N. F. Scherer, and A. M. Weiner, eds., Springer Ser. Chem.
Phys. 71, 247–249 (Springer, Berlin, 2003).
iii[3] R. Grunwald et al., “Femtosecond laser beam shaping with structured thin-
film elements,” In Applications of Photonic Tchnology 5, R. A. Lessard, G. A.
Lampropoulos, and G. W. Schinn, eds., Proceedings of SPIE 4833, 354–361
(2002).
[4] V.Kozic, W.Wernke, J.Dreyer, K.W.Brzezinka, M.Rini, A.Kummrow, and
T. Elsaesser, “Vibrational excitation and energy redistribution after ultrafast
internal conversion in 4-nitroaniline,” J. Chem. Phys. 117, 719–726 (2002).
[5] M. Krikunova, A. Kummrow, B. Voigt, M. Rini, H. Lokstein, A. Moskalenko,
H. Scheer, A. Razjivin, and D. Leupold, “Fluorescence of native and
carotenoid-depleted LH2 from Chromatium minutissimum, originating from
simultaneous two-photon absorption in the spectral range of the presumed
(optically dark) S state of carotenoids,” FEBS Lett. 528, 227–229 (2002).1
[6] R. Grunwald, U. Griebner, E. T. J. Nibbering, A. Kummrow, M. Rini, T.
Elsaesser, V. Kebbel, H. J. Hartmann, and W. Jüptner, “Spatially resolved
small-angle noncollinear interferometric autocorrelation of ultrashort pulses
with microaxicon arrays,” J. Opt. Soc. Am. A 18, 2923–2931 (2001).
ivvviContents
1 Introduction 3
2 Ultrafast vibrational spectroscopy of photoinduced reactions 11
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
2.2 UV-pump IR-probe spectroscopy with frequency selective detection 12
2.3 Effects of coherence: the perturbed free-induction decay . . . . . . 15
2.4 of anharmonicity . . . . . . . . . . . . . . . . . . . . . . . 21
2.5 Effects of rotational relaxation . . . . . . . . . . . . . . . . . . . . 27
3 Experimental 31
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
3.2 The laser system . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
3.3 Nonlinear parametric conversion . . . . . . . . . . . . . . . . . . . 33
3.3.1 Femtosecond infrared pulses . . . . . . . . . . . . . . . . . 33
3.3.2 Femtosecond ultraviolet pulses . . . . . . . . . . . . . . . . 36
3.4 Pump-probe experiments . . . . . . . . . . . . . . . . . . . . . . . 38
4 Intramolecular excited state hydrogen transfer 45
4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.2 2-(2’-hydroxyphenyl)benzothiazole (HBT) . . . . . . . . . . . . . 49
4.3 Experimental results . . . . . . . . . . . . . . . . . . . . . . . . . 52
4.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
4.4.1 Ultrafast formation of the keto tautomer . . . . . . . . . . 59
4.4.2 Coherence phenomena in photoinduced chemical reactions 61
4.4.3 Vibrationalrelaxationprocessesinducedbyhydrogentransfer 64
4.5 Summary and conclusions . . . . . . . . . . . . . . . . . . . . . . 66
5 Intermolecular excited state proton transfer 69
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
5.2 Excited state proton transfer from HPTS . . . . . . . . . . . . . . 74
5.3 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . 77
5.3.1 Proton transfer in hydrogen-bonded complexes . . . . . . . 86
5.3.2 Diffusion limited proton transfer . . . . . . . . . . . . . . . 88
12 CONTENTS
5.4 General mechanism for an acid-base reaction . . . . . . . . . . . . 90
6 Ring opening reaction of photochromic compounds 95
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
6.2 Photochromic spiropyrans . . . . . . . . . . . . . . . . . . . . . . 97
6.3 Ring opening reaction of BIPS . . . . . . . . . . . . . . . . . . . . 99
6.3.1 Experimental results . . . . . . . . . . . . . . . . . . . . . 101
6.3.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
6.4 Ring opening reaction of 6-nitro-BIPS . . . . . . . . . . . . . . . 109
6.4.1 Experimental results . . . . . . . . . . . . . . . . . . . . . 110
6.4.2 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
6.5 Summary and Conclusions . . . . . . . . . . . . . . . . . . . . . . 116
7 Summary and Conclusions 119
References 123
Acknowledgements 137
Zusammenfassung 139