Photosynthetic Excitons

The following sections are included:

• Preface

• Contents

The following sections are included:

• Introduction
  • Disordered vs. ordered light-harvesting systems

• The Photosynthetic Pigments: Chlorophylls, Bacteriochlorophylls and Carotenoids
  • The chlorophylls
  • The bacteriochlorophylls
  • The carotenoids

• The Structure and Function of Important Photosynthetic Pigment-Protein Complexes
  • The bacterial photosynthetic reaction center
  • The reaction centers of Photosystem II and Photosystem I
  • The peripheral light-harvesting complex (LH2) of photosynthetic purple bacteria
  • The Fenna-Matthews-Olson protein of green sulphur bacteria
  • LHCII, the major chlorophyll binding light-harvesting complex of plants
  • The core antenna and reaction center of Photosystem I

• Mechanism of Energy Transfer and Trapping in Photosynthesis
  • The Förster equation
  • Trapping by the reaction center

• Energy transfer in Some Photosynthetic Systems
  • Energy transfer in the peripheral and core antennae of photosynthetic purple bacteria
  • Energy transfer in the Fenna-Matthews-Olson complex
  • Energy transfer in the major peripheral plant light-harvesting complex LHCII
  • Energy transfer in Photosystem I

• Conclusions

• References

The following sections are included:

• Historical Overview

• Interactions between Molecules

• The Excitonically Coupled Dimer
  • Non-equivalent site energies
  • Transition dipole moment

• Excitonic Interactions in Larger Systems

• Molecular Crystals

• Molecular and Lattice Vibrations and Loss of Exciton Coherence

• References

The following sections are included:

• Introduction

• Linear Dichroism

• Circular Dichroism
  • The CD of a dimer

• Fluorescence

• Fluorescence Anisotropy

• Transient Absorption (Pump-Probe)

• Triplet-minus-Singlet Spectroscopy

• Stark Spectroscopy

• A Hypothetical Dimer

• B820: An Excitonically Coupled Dimer from Photosynthetic Purple Bacteria

• Spectroscopic Properties of B820

• Appendix
  • Derivation of Expressions for Linear Dichroism
  • Derivation of Expression for Anisotropy

• References

The following sections are included:

• Introduction

• Absorption
  • Ground-state absorption
  • Excited-state absorption and transient absorption
  • Non-degenerate dimer

• Circular Dichroism

• Circular Dichroism of B820

• References

The following sections are included:

• Introduction

• The Coupling of Vibrations and Phonons to Electronic Transitions
  • Adiabatic approach
  • Transition dipole moment
  • Absorption spectrum
  • Electron-phonon coupling
  • Brownian oscillator model

• Homogeneous and Inhomogeneous Broadening

• Exciton Coupling and Spectral Broadening

• Spectral Moments

• Hole Burning

• Fluorescence Line Narrowing

• Separation of the Broadening Contributions for the FMO Complex

• Appendix
  • The Harmonic Oscillator
  • The Response Function
  • Spectral Moments for Inhomogeneously Broadened Excitonic Spectra
  • Spectral Moments for Homogeneously Broadened Excitonic Spectra

• References

The following sections are included:

• Introduction

• Molecular Crystals

• Cyclic Molecular Aggregates

• Linear Molecular Aggregates (J-Aggregates)

• Effect of Disorder on the Exciton Spectrum

• Exciton-Phonon Interaction and Exciton Self-Trapping

• Optical Transitions
  • Transition dipole strength and selection rules
  • Exciton absorption bandshape

• Exciton Migration

• Appendix
  • Eigenfunctions of Linear Aggregates

• References

The following sections are included:

• Introduction

• Correlation of Structural and Spectroscopic Properties of Photosynthetic Reaction Centers
  • The bacterial reaction center
  • Polarized spectroscopy of crystals of the reaction center of Rhodopseudomonas viridis
  • Calculation of the absorption spectra
  • Vibronic coupling in the bacterial reaction center
  • Charge-transfer states
  • The multimeric exciton model for the Photosystem II reaction center
  • Theoretical methods
  • Exciton calculations
  • Exciton delocalization and energetic disorder
  • The multimer model of P680: Comparison with experiment
  • “P680”
  • Photosystem I

• Excitonic Interactions in Light-Harvesting Pigment-Proteins
  • LH2
  • The structure of LH2 of Rhodopseudomonas acidophila and Rhodospirillum molischianum
  • Spectroscopic properties of LH1 and LH2
  • Calculation of the spectroscopic properties of LH2 and LH1
  • Diagonal disorder and the dipole strength of the lowest exciton state of LH2
  • Localization of the exciton in the presence of static and dynamic disorder
  • Calculation of the LH2 CD spectrum using exciton theory
  • The BCh1 a binding protein of green photosynthetic sulphur bacteria (the Fenna-Matthews-Olson complex)

• The Major Ch1 a-Ch1 b Light-Harvesting Complex of Green Plants (or LHCII)

• Appendix 7.1: Carotenoid-Chlorophyll Interactions in LHCII

• References

The following sections are included:

• Introduction

• Coherent vs. Incoherent Excitons

• Stochastic Liouville Equation

• Depolarization for a Dimer as Described by the Stochastic Liouville Equation

• Migration of Localized Excitations: The Förster Equation

• Generalized Master Equation

• Exciton Relaxation

• Reference

The following sections are included:

• Introduction

• C-Phycocyanin

• Allophycocyanin

• Peridinin-Chlorophyll-a-Protein from Dinoflagellates

• The FMO Complex from Green Bacteria

• Light-Harvesting Complex II from Green Plants

• Dynamics of Energy Transfer in LH1 and LH2 of Photosynthetic Purple Bacteria
  • Energy transfer among the B800 bacteriochlorophylls in LH2
  • B800 to B850 energy transfer
  • Energy transfer within the strongly coupled B850 ring
  • Interactions and energy transfer between carotenoid and bacteriochlorophyll molecules of LH2

• References

The following sections are included:

• Introduction

• Excitation Trapping by Reaction Centers
  • Kinetic model
  • Average-lifetime approach
  • Longest-decay-time approach
  • Perturbed-two-level model
  • Comparison of the models

• Application to Bacterial Photosynthesis
  • Local-trap approximation
  • Perturbed two-level approximation
  • Interpretation of the effective trapping rate
  • Comparison to standardized models

• Application to Plant Systems
  • Excitation trapping in PSI
  • Application to PSII

• Concluding Remarks

• Appendix
  • The Trap as a Local Perturbation of a Lattice
  • The Perturbed Two-Level Model
  • Averaged Orientation Factor in Exciton Transfer

• References

The following sections are included:

• Introduction

• The Bacterial PSU — Energy Transfer over the Antenna Network and Trapping by the Reaction Center

• Photosystem II
  • Organization
  • Trapping in PSII cores

• Energy Transfer Dynamics and Trapping in Intact PSII

• Energy Transfer and Trapping in the Core Antenna of Photosystem I
  • Organization and structure
  • Steady-state spectroscopic properties
  • Time-resolved excitation decay at room temperature
  • Trapping in the Photosystem I core complex
  • Trapping in large Photosystem I complexes
  • Excitation decay in intact Photosystem I
  • Spectral and spatial equilibration in Photosystem I
  • Energy transfer in Photosystem I at low temperatures

• Concluding Remarks

• References

The following sections are included:

• Introduction

• Annihilation in Large Aggregates
  • Mathematical formulation of the kinetic equations
  • Analysis of kinetic equations
  • Nonlinear excitation quenching
  • Quasi-linear excitation quenching
  • Fractal model for spectrally inhomogeneous aggregates

• Small Aggregates
  • Distribution function approach
  • Statistical approach
  • Coherent excitons

• Singlet-Triplet Annihilation
  • Singlet excitation trapping by triplets
  • Fluorescence induction and S–T annihilation

• Local Heating During Annihilation
  • Dissipation of vibrational-mode energy
  • Modulation of the nuclear motion

• Excitation Annihilation Studied by Pump–Probe Spectroscopy
  • Higher excited state relaxation
  • Excitation correlation effects
  • Local temperature effect

• Kinetic Equations of the S–S Annihilation

• Distribution Function Approach for Three-Molecular Aggregate

• References

The following sections are included:

• Introduction

• Fluorescence Quantum Yield Measurements

• Annihilation Kinetics in Chromatophores

• Fenna-Matthews-Olson Complex

• Annihilation Kinetics in LHCII Complex

• The Effect of S-T Annihilation on Fluorescence Induction in PSII

• References

The following sections are included:

• Introduction
  • Linear response
  • Multi-wave mixing
  • Nonlinear optical response

• Response Functions in Multilevel Systems

• Experiments on Energy Transfer and Electron Transfer in Photosynthesis Applying Nonlinear Femtosecond Spectroscopy
  • The 3PEPS method
  • 3PEPS experiments on LH1 and LH2 complexes of Rhodobacter sphaeroides
  • 3PEPS experiments on the accessory pigments in the RC of Rhodobacter sphaeroides

• Appendix
  • Fourier Transformation

• References

• Subject Index