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Introduction Figure 1.7: Absorption (dash) emission and (solid) spectra for Anthracene (in Toluene). Excitation light source 350 nm. The numbers 0,1 and 2 refer to vibrational energy levels. Figure 1.8: Typical fluorophores present in crude oil and their emission maximum. Reproduced from [41]. 16
Introduction The peaks in the absorption spectrum correspond to transitions from the lowest vibrational level of the electronic ground state to different vibrational levels of the first electronic excited state, while the peaks observed in the fluorescence spectrum arise from transitions from the lowest vibrational level of the excited electronic state to the different vibrational levels of the ground state. As shown in Figure 1.7, there is some overlap of the absorption and emission spectra because at room temperature a small fraction of the molecules are in a vibrational level higher than 0. At cryogenic temperatures, this overlap would be reduced [37]. Larger molecules will typically have more complex electronic spectra, emitting at longer wavelengths. For example, in large PAH’s, the degree of conjugation increases, the number of delocalised π orbitals increases. Increased delocalisation reduces the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO). Since the absorption energy is reduced, a shift of the absorption and emission to longer wavelengths occurs (Figure 1.8). 1.2.3 Kinetics of photophysical processes Fluorescence quantum yield and lifetime are perhaps the two most important phys- ical emission characteristics of a fluorophore [36]. Quantum yield (Equation 1.2) is defined as the number of emitted photons relative to the number of absorbed photons: φ = number of fluorescent events number of photons absorbed Intensity of fluorescence If = = Intensity of light absorbed Iabs (1.2) To develop expressions for quantum yield and lifetime, consider the formation and decay of the excited state: Absorption : S + hνex −→ S ∗ F luorescence : S ∗ −→ S + hνem υabs = Iabs υf = kf[S ∗ ] Internal conversion : S ∗ −→ S υic = kic[S ∗ ] Intersystem crossing : S ∗ −→ T ∗ 17 υisc = kisc[S ∗ ]
Page 1 and 2: Time-Resolved Fluorescence Spectros
Page 3 and 4: Abstract behaviour allowing calcula
Page 5 and 6: Contents List of Publications and P
Page 7 and 8: Contents 2.3 Temperature based Life
Page 9 and 10: List of Publications and Presentati
Page 11 and 12: Abbreviations Abbrev Definition API
Page 13 and 14: Chapter 1 Introduction For many yea
Page 15 and 16: Introduction temperature increases
Page 17 and 18: A seal or cap-rock that prevents th
Page 19 and 20: Introduction Figure 1.2: Crude oil
Page 21 and 22: Introduction eroatoms (O, S, N) and
Page 23 and 24: Introduction toluene, dichlorometha
Page 25 and 26: 1.2 Fluorescence Spectroscopy 1.2.1
Page 27: Introduction S1 state for a certain
Page 31 and 32: Introduction Figure 1.9: Jablonski
Page 33 and 34: Introduction Figure 1.10: Static qu
Page 35 and 36: Introduction the ratio of τ 0/τ i
Page 37 and 38: 1.2.5 Measuring fluorescence lifeti
Page 39 and 40: Introduction Figure 1.14: Time-reso
Page 41 and 42: Introduction The autocorrelation fu
Page 43 and 44: Introduction case, the molecules ex
Page 45 and 46: From Equation 1.26, Introduction ω
Page 47 and 48: m = 1 P 2 + Q 2 Introduction (1.36
Page 49 and 50: Introduction based average lifetime
Page 51 and 52: Introduction Figure 1.21: General p
Page 53 and 54: Introduction TAC output pulse is gi
Page 55 and 56: Introduction at each frequency acco
Page 57 and 58: Introduction diagram showing the op
Page 59 and 60: Introduction Figure 1.26: Schematic
Page 61 and 62: Introduction provides enhanced cont
Page 63 and 64: Introduction PAH’s. It has been s
Page 65 and 66: to heavy oils (low API gravity). In
Page 67 and 68: Introduction The balance between en
Page 69 and 70: Introduction Figure 1.34: Fluoresce
Page 71 and 72: Introduction used [126, 129, 132] a
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Page 75 and 76: fractional contributions over time
Page 77 and 78: Introduction concentration and Ksv
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Introduction Figure 1.38: Fluoresce
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Introduction Figure 1.39: Fluoresce
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1.5 Crude oil photophysics Introduc
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Introduction stages of thermal matu
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Introduction yellow to red fluoresc
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1.7 Thesis goal Introduction This i
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Materials and Methods concentration
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Table 2.2: Fractionation Data for B
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Materials and Methods 2.2 Frequency
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Materials and Methods was within ±
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Materials and Methods The dichroic
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Figure 2.5: Transmission characteri
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Materials and Methods Figure 2.7: S
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Materials and Methods The variation
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Materials and Methods Figure 2.9: L
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Materials and Methods Figure 2.10:
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Materials and Methods Comparison ca
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Materials and Methods with ρ param
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Materials and Methods 2.3 Temperatu
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Materials and Methods IRF of the sy
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Materials and Methods 2.4 Temperatu
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Materials and Methods a series of w
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Materials and Methods 2. Using the
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Lifetime study on crude oils by the
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Table 3.3: Average lifetime and sin
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Table 3.5: Average lifetime and sin
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3.5 Single Lifetime distributions L
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Energy Transfer and Quenching proce
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Influence of low temperature on flu
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Conclusions and Future Work model (
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Appendix A Reference Lifetime Stand
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Appendix Figure A.2: FD response fo
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A.3 SPA N-(3-sulfopropyl) acridiniu
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A.4 Rhodamine B Appendix Rhodamine
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A.5 Acridone Appendix The highly ph
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Appendix Figure A.11: FD response f
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Table B.1: Frequency Domain average
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Appendix Table B.3: Emission λmax
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Table B.5: Frequency Domain lifetim
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Appendix for the determination of t
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Appendix Figure C.3: Multifrequency
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Appendix Figure C.5: FLIM intensity
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Appendix Table C.1: Fluorescence li
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Appendix D Published Work 281
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998 J Fluoresc (2008) 18:997-1006 s
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1000 J Fluoresc (2008) 18:997-1006
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1002 J Fluoresc (2008) 18:997-1006
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1004 J Fluoresc (2008) 18:997-1006
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1006 J Fluoresc (2008) 18:997-1006
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Bibliography [10] W. G. Dow (1977),
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Bibliography [31] M. A. Ali and W.
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Bibliography [53] R. D. Spencer and
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Bibliography [75] K. Konig (2000),
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Bibliography [93] C. Pasquini and A
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Bibliography [113] C. Ralston, X. W
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Bibliography [132] A. Ryder (2004),
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Bibliography variable-angle synchro
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Bibliography [171] R. K. McLimans (
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Bibliography using fluorescence spe
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Bibliography [210] H. Mishra, S. Pa
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Bibliography [229] N. Boens, W. W.
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