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9789810232801

Photosynthetic Excitons

by ; ;
  • ISBN13:

    9789810232801

  • ISBN10:

    9810232802

  • Format: Hardcover
  • Copyright: 1997-09-01
  • Publisher: WORLD SCIENTIFIC PUB CO INC
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Summary

Excitons are considered as the basic concept used by describing the spectral properties of photosynthetic pigment-protein complexes and excitation dynamics in photosynthetic light-harvesting antenna and reaction centers. Following the recently obtained structures of a variety of photosynthetic pigment-protein complexes from plants and bacteria our interest in understanding the relation between structure, function and spectroscopy has strongly increased. These data demonstrate a short interpigment distance (of the order of 1 nm or even smaller) and/or a highly symmetric (ring-like) arrangement of pigment molecules in peripheral light-harvesting complexes of photosynthetic bacteria. Books which were devoted to the exciton problem so far mainly considered the spectral properties of molecular crystals. However, the small size of these pigment aggregates in the pigment-protein complexes as well as the role of the protein, which is responsible for the structural arrangement of the complex, clearly will have a dramatic influence on the pigment spectra and exciton dynamics. All these aspects of the problem are considered in this book. Exciton theory is mainly considered for small molecular aggregates (dimers, ring-like structures etc.). Together with the theoretical description of the classical conceptual approach, which mainly deals with polarization properties of the absorption and fluorescence spectra, the nonlinear femtosecond spectroscopy which is widely used for investigations now is also discussed. A large part of the book demonstrates the excitonic effects in a multitude of photosynthetic pigment-protein complexes and how we can understand these properties on the basis of the excitonconcept.

Table of Contents

Preface v
Introduction: Structural Organization, Spectral Properties and Excitation Energy Transfer in Photosynthesis
1(46)
Introduction
1(1)
Disordered vs. ordered light-harvesting systems
2(1)
The Photosynthetic Pigments: Chlorophylls, Bacteriochlorophylls and Carotenoids
2(9)
The chlorophylls
3(3)
The bacteriochlorophylls
6(2)
The carotenoids
8(3)
The Structure and Function of Important Photosynthetic Pigment-Protein Complexes
11(11)
The bacterial photosynthetic reaction center
12(3)
The reaction centers of Photosystem II and Photosystem I
15(1)
The peripheral light-harvesting complex (LH2) of photosynthetic purple bacteria
15(3)
The Fenna-Matthews-Olson protein of green sulphur bacteria
18(1)
LHCII, the major chlorophyll binding light-harvesting complex of plants
19(2)
The core antenna and reaction center of Photosystem 1
21(1)
Mechanism of Energy Transfer and Trapping in Photosynthesis
22(6)
The Forster equation
22(1)
Trapping by the reation center
23(5)
Energy Transfer in Some Photosynthetic Systems
28(9)
Energy transfer in the peripheral and core antennae of photosynthetic purple bacteria
28(4)
Energy transfer in the Fenna-Matthews-Olson complex
32(1)
Energy transfer in the major peripheral plant light-harvesting complex LHCII
33(2)
Energy transfer in Photosystem 1
35(2)
Conclusions
37(10)
References
38(9)
The Exciton Concept
47(26)
Historical Overview
47(1)
Interactions between Molecules
48(2)
The Excitonically Coupled Dimer
50(12)
Non-equivalent site energies
53(2)
Transition dipole moment
55(7)
Excitonic Interactions in Larger Systems
62(6)
Molecular Crystals
68(1)
Molecular and Lattice Vibrations and Loss of Exciton Coherence
69(4)
References
71(2)
Some Optical Properties of the Excitonically Coupled Dimer
73(46)
Introduction
73(1)
Linear Dichroism
74(5)
Circular Dichroism
79(2)
The CD of a dimer
81(1)
Fluorescence
81(4)
Fluorescence Anisotropy
85(4)
Transient Absorption (Pump-Probe)
89(6)
Triplet-minus-Singlet Spectroscopy
95(1)
Stark Spectroscopy
96(4)
A Hypothetical Dimer
100(4)
B820: An Excitonically Coupled Dimer from Photosynthetic Purple Bacteria
104(1)
Spectroscopic Properties of B820
105(14)
Derivation of Expressions for Linear Dichroism
113(2)
Derivation of Expression for Anisotropy
115(2)
References
117(2)
Mixing with Higher Excited States
119(20)
Introduction
119(1)
Absorption
119(10)
Ground-state absorption
119(3)
Excited-state absorption and transient absorption
122(4)
Non-degenerate dimer
126(3)
Circular dichroism
129(6)
Circular dichroism of B820
135(4)
References
138(1)
Spectral Shapes: Homogeneous and Inhomogeneous Broadening
139(58)
Introduction
139(1)
The Coupling of Vibrations and Phonons to Electronic Transitions
139(14)
Adiabatic approach
140(4)
Transition dipole moment
144(3)
Absorption spectrum
147(3)
Electron-phonon coupling
150(1)
Brownian oscillator model
151(2)
Homogeneous and Inhomogeneous Broadening
153(3)
Exciton Coupling and Spectral Broadening
156(3)
Spectral Moments
159(5)
Hole Burning
164(4)
Fluorescence Line Narrowing
168(1)
Separation of the Broadening Contributions for the FMO Complex
169(28)
The Harmonic Oscillator
176(8)
The Response Function
184(4)
Spectral Moments for Inhomogeneously Broadened Excitonic Spectra
188(2)
Spectral Moments for Homogeneously Broadened Excitonic Spectra
190(5)
References
195(2)
Spectroscopy of Excitions in Molecular Crystals and Aggregates
197(44)
Introduction
197(1)
Molecular Crystals
197(6)
Cyclic Molecular Aggregates
203(4)
Linear Molecular Aggregates (J-Aggregates)
207(1)
Effect of Disorder on the Exciton Spectrum
208(8)
Exciton-Phonon Interaction and Exciton Self-Trapping
216(4)
Optical Transitions
220(11)
Transition dipole strength and selection rules
220(10)
Exciton absorption bandshape
230(1)
Exciton Migration
231(10)
Eigenfunctions of Linear Aggregates
237(1)
References
238(3)
Excitonic Interactions in Photosynthetic Systems: Spectroscopic Evidence
241(70)
Introduction
241(1)
Correlation of Structural and Spectroscopic Properties of Photosynthetic Reaction Centers
241(32)
The bacterial reaction center
241(2)
Polarized spectroscopy of crystals of the reaction center of Rhodopseudomonas viridis
243(2)
Calculation of the absorption spectra
245(3)
Vibronic coupling in the bacterial reaction center
248(4)
Charge-transfer states
252(9)
The multimeric exciton model for the Photosystem II reaction center
261(2)
Theoretical methods
263(1)
Exciton calculations
264(1)
Exciton delocalization and energetic disorder
265(2)
The multimer model of P680: Comparison with experiment
267(1)
``P680''
268(2)
Photosystem I
270(3)
Excitonic Interactions in Light-Harvesting Pigment-Proteins
273(24)
LH2
273(1)
The Structure of LH2 of Rhodopseudomonas acidophila and Rhodospirillum molischianum
274(2)
Spectroscopic properties of LH1 and LH2
276(3)
Calculation of the spectroscopic properties of LH2 and LH1
279(2)
Diagonal disorder and the dipole strength of the lowest exciton state of LH2
281(2)
Localization of the exciton in the presence of static and dynamic disorder
283(2)
Calculation of the LH2 CD spectrum using exciton theory
285(3)
The BChl a binding protein of green photosynthetic sulphur bacteria (the Fenna-Matthews-Olson complex)
288(9)
The Major Chl a-Chl b Light-Harvesting Complex of Green Plants (or LHCII)
297(14)
Carotenoid-Chlorophyll Interactions in LHCII
304(1)
References
305(6)
Exciton Dynamics
311(36)
Introduction
311(1)
Coherent vs. Incoherent Excitons
311(5)
Stochastic Liouville Equation
316(7)
Depolarization for a Dimer as Described by the Stochastic Liouville Equation
323(6)
Migration of Localized Excitations: The Forster Equation
329(4)
Generalized Master Equation
333(4)
Exciton Relaxation
337(10)
References
344(3)
Exciton Dynamics in Different Antenna Complexes. Coherence and Incoherence
347(54)
Introduction
347(1)
C-Phycocyanin
347(5)
Allophycocyanin
352(5)
Peridinin-Chlorophyll-a-Protein from Dinoflagellates
357(6)
The FMO Complex from Green Bacteria
363(9)
Light-Harvesting Complex II from Green Plants
372(3)
Dynamics of Energy Transfer in LH1 and LH2 of Photosynthetic Purple Bacteria
375(26)
Energy transfer among the B800 bacteriochlorophylls in LH2
376(3)
B800 to B850 energy transfer
379(2)
Energy transfer within the strongly coupled B850 ring
381(6)
Interactions and energy transfer between carotenoid and bacteriochlorophyll molecules of LH2
387(6)
References
393(8)
Migration of Localized Excitons: Forster Excitation Energy Transfer and Trapping by Reaction Centers
401(48)
Introduction
401(1)
Excitation Trapping by Reaction Centers
402(13)
Kinetic model
404(1)
Average-lifetime approach
405(3)
Longest-decay-time approach
408(1)
Perturbed-two-level model
409(3)
Comparison of the models
412(3)
Application to Bacterial Photosynthesis
415(9)
Local-trap approximation
416(1)
Perturbed two-level approximation
417(2)
Interpretation of the effective trapping rate
419(2)
Comparison to standardized models
421(3)
Application to Plant Systems
424(10)
Excitation trapping in PSI
424(6)
Application to PSII
430(4)
Concluding Remarks
434(15)
The Trap as a Local Perturbation of a Lattice
437(3)
The Perturbed Two-Level Model
440(4)
Averaged Orientation Factor in Exciton Transfer
444(1)
References
445(4)
Excitation Energy Transfer and Trapping Experiments
449(30)
Introduction
449(1)
The Bacterial PSU --- Energy Transfer over the Antenna Network and Trapping by the Reaction Center
449(4)
Photosystem II
453(3)
Organization
453(2)
Trapping in PSII cores
455(1)
Energy Transfer Dynamics and Trapping in Intact PSII
456(2)
Energy Transfer and Trapping in the Core Antenna of Photosystem I
458(12)
Organization and structure
459(1)
Steady-state spectroscopic properties
460(1)
Time-resolved excitation decay at room temperature
461(1)
Trapping in the Photosystem I core complex
462(3)
Trapping in large Photosystem I complexes
465(1)
Excitation decay in intact Photosystem I
465(1)
Spectral and spatial equilibration in Photosystem I
465(2)
Energy transfer in Photosystem 1 at low temperatures
467(3)
Concluding Remarks
470(9)
References
472(7)
Nonlinear Annihilation of Excitons, Theory
479(44)
Introduction
479(1)
Annihilation in Large Aggregates
480(10)
Mathematical formulation of the kinetic equations
481(2)
Analysis of Kinetic equations
483(2)
Nonlinear excitation quenching
485(2)
Quasi-linear excitation quenching
487(1)
Fractal model for spectrally inhomogeneous aggregates
488(2)
Small Aggregates
490(5)
Distribution function approach
490(1)
Statistical approach
491(3)
Coherent excitons
494(1)
Singlet-Triplet Annihilation
495(8)
Singlet excitation trapping by triplets
495(2)
Fluorescence induction and S--T annihilation
497(6)
Local Heating During Annihilation
503(3)
Dissipation of vibrational-mode energy
503(2)
Modulation of the nuclear motion
505(1)
Excitation Annihilation Studied by Pump-Probe Spectroscopy
506(17)
Higher excited state relaxation
507(1)
Excitation correlation effects
508(1)
Local temperature effect
509(1)
Kinetic Equations of the S--S Annihilation
510(6)
Distribution Function Approach for Three-Molecular Aggregate
516(3)
References
519(4)
Nonlinear Annihilation of Excitons, Experimental
523(28)
Introduction
523(1)
Fluorescence Quantum Yield Measurements
523(7)
Annihilation Kinetics in Chromatophores
530(5)
Fenna--Matthews--Olson Complex
535(3)
Annihilation Kinetics in LHCII Complex
538(8)
The Effect of S--T Annihilation on Fluorescence Induction in PSII
546(5)
References
548(3)
Nonlinear Spectroscopy
551(34)
Introduction
551(17)
Linear response
552(5)
Multi-wave mixing
557(3)
Nonlinear optical response
560(8)
Response Functions in Multilevel Systems
568(7)
Experiments on Energy Transfer and Electron Transfer in Photosynthesis Applying Nonlinear Femtosecond Spectroscopy
575(10)
The 3PEPS method
575(3)
3PEPS experiments on LH1 and LH2 complexes of Rhodobacter sphaeroides
578(2)
3PEPS experiments on the accessory pigments in the RC of Rhodobacter sphaeroides
580(2)
Fourier Transformation
582(1)
References
583(2)
Subject Index 585

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