The effect of correlated bath fluctuations on exciton transfer.

Excitation dynamics of various light harvesting systems have been investigated with many theoretical methods including various non-Markovian descriptions of dissipative quantum dynamics. It is typically assumed that each excited state is coupled to an independent thermal environment, i.e., that fluctuations in different environments are uncorrelated. Here the assumption is dropped and the effect of correlated bath fluctuations on excitation transfer is investigated. Using the hierarchy equations of motion for dissipative quantum dynamics it is shown for models of the B850 bacteriochlorophylls of LH2 that correlated bath fluctuations have a significant effect on the LH2→LH2 excitation transfer rate. It is also demonstrated that inclusion of static disorder is crucial for an accurate description of transfer dynamics.

[1]  Klaus Schulten,et al.  Excitation migration in trimeric cyanobacterial photosystem I. , 2004, The Journal of chemical physics.

[2]  G. Fleming,et al.  Theoretical examination of quantum coherence in a photosynthetic system at physiological temperature , 2009, Proceedings of the National Academy of Sciences.

[3]  T. Ritz,et al.  Influence of subunit structure on the oligomerization state of light-harvesting complexes: A free energy calculation study , 2005, physics/0504213.

[4]  A. Gall,et al.  Static and dynamic protein impact on electronic properties of light-harvesting complex LH2. , 2008, The journal of physical chemistry. B.

[5]  Akihito Ishizaki,et al.  Dynamics of a multimode system coupled to multiple heat baths probed by two-dimensional infrared spectroscopy. , 2007, The journal of physical chemistry. A.

[6]  Klaus Schulten,et al.  Coupling of protein motion to electron transfer in a photosynthetic reaction center: investigating the low temperature behavior in the framework of the spin—boson model , 1994 .

[7]  Graham R. Fleming,et al.  Influence of phonons on exciton transfer dynamics: comparison of the Redfield, Förster, and modified Redfield equations , 2002 .

[8]  Christoph Meier,et al.  Non-Markovian evolution of the density operator in the presence of strong laser fields , 1999 .

[9]  Tõnu Pullerits,et al.  Picosecond dynamics of directed excitation transfer in spectrally heterogeneous light-harvesting antenna of purple bacteria , 1989 .

[10]  Leonas Valkunas,et al.  Protein dynamics revealed in the excitonic spectra of single LH2 complexes , 2007 .

[11]  Patrick Rebentrost,et al.  Non-Markovian quantum jumps in excitonic energy transfer. , 2009, The Journal of chemical physics.

[12]  Seogjoo J. Jang,et al.  Multichromophoric Förster resonance energy transfer. , 2004, Physical review letters.

[13]  S. Mukamel,et al.  Two‐exciton spectroscopy of photosynthetic antenna complexes: Collective oscillator analysis , 1996 .

[14]  A. Leggett,et al.  Quantum tunnelling in a dissipative system , 1983 .

[15]  Klaus Schulten,et al.  Atomic-level structural and functional model of a bacterial photosynthetic membrane vesicle , 2007, Proceedings of the National Academy of Sciences.

[16]  Rienk van Grondelle,et al.  Dynamics of the emission spectrum of a single LH2 complex: interplay of slow and fast nuclear motions. , 2006, Biophysical journal.

[17]  A. Ishizaki,et al.  Quantum Dynamics of System Strongly Coupled to Low-Temperature Colored Noise Bath: Reduced Hierarchy Equations Approach , 2005 .

[18]  A. G. Redfield,et al.  The Theory of Relaxation Processes , 1965 .

[19]  U. Weiss.  Quantum Dissipative Systems , 1993 .

[20]  K. Schulten,et al.  Quest for spatially correlated fluctuations in the FMO light-harvesting complex. , 2011, The journal of physical chemistry. B.

[21]  V. May,et al.  Ultrafast Exciton Motion in Photosynthetic Antenna Systems: The FMO-Complex , 1998 .

[22]  O. Kühn,et al.  Two-dimensional vibrational spectroscopy of a double minimum system in a dissipative environment , 2003 .

[23]  YiJing Yan,et al.  Quantum mechanics of dissipative systems. , 2005, Annual review of physical chemistry.

[24]  N. Demirdöven,et al.  Correlated vibrational dynamics revealed by two-dimensional infrared spectroscopy. , 2002, Physical review letters.

[25]  T. Mančal,et al.  Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems , 2007, Nature.

[26]  G. Fleming,et al.  Unified treatment of quantum coherent and incoherent hopping dynamics in electronic energy transfer: reduced hierarchy equation approach. , 2009, The Journal of chemical physics.

[27]  G. Fleming,et al.  On the adequacy of the Redfield equation and related approaches to the study of quantum dynamics in electronic energy transfer. , 2009, The Journal of chemical physics.

[28]  K. Schulten,et al.  Light harvesting complex II B850 excitation dynamics. , 2009, The Journal of chemical physics.

[29]  Alexander Eisfeld,et al.  Influence of complex exciton-phonon coupling on optical absorption and energy transfer of quantum aggregates. , 2009, Physical review letters.

[30]  Rienk van Grondelle,et al.  Energy transfer in photosynthesis: experimental insights and quantitative models. , 2006, Physical chemistry chemical physics : PCCP.

[31]  G. Fleming,et al.  Excitation Transfer in the Core Light-Harvesting Complex (LH-1) of Rhodobacter sphaeroides: An Ultrafast Fluorescence Depolarization and Annihilation Study , 1995 .

[32]  M. Elstner,et al.  Solvent fluctuations drive the hole transfer in DNA: a mixed quantum-classical study. , 2009, The journal of physical chemistry. B.

[33]  Govindjee.  Bioenergetics of photosynthesis , 1975 .

[34]  Michael Schreiber,et al.  Calculation of absorption spectra for light-harvesting systems using non-Markovian approaches as well as modified Redfield theory. , 2006, The Journal of chemical physics.

[35]  Animesh Datta,et al.  Highly efficient energy excitation transfer in light-harvesting complexes: The fundamental role of n , 2009, 0901.4454.

[36]  J. Eckel,et al.  Quantum coherent biomolecular energy transfer with spatially correlated fluctuations , 2010, 1003.3857.

[37]  R. Silbey,et al.  Shared-mode assisted resonant energy transfer in the weak coupling regime. , 2009, The Journal of chemical physics.

[38]  Ping Cui,et al.  Exact quantum master equation via the calculus on path integrals. , 2005, The Journal of chemical physics.

[39]  A. Nazir.  Correlation-dependent coherent to incoherent transitions in resonant energy transfer dynamics. , 2009, Physical review letters.

[40]  A. Dijkstra,et al.  Correlated fluctuations in the exciton dynamics and spectroscopy of DNA , 2010, 1004.1453.

[41]  Klaus Schulten,et al.  Excitons in a photosynthetic light-harvesting system: a combined molecular dynamics, quantum chemistry, and polaron model study. , 2001, Physical review. E, Statistical, nonlinear, and soft matter physics.

[42]  J. Köhler,et al.  Low-temperature single-molecule spectroscopy on photosynthetic pigment–protein complexes from purple bacteria , 2009, Photosynthesis Research.

[43]  K. Schulten,et al.  General random matrix approach to account for the effect of static disorder on the spectral properties of light harvesting systems. , 2002, Physical review. E, Statistical, nonlinear, and soft matter physics.

[44]  Volkhard May,et al.  Charge and Energy Transfer Dynamics in Molecular Systems: A Theoretical Introduction , 2000 .

[45]  S. Mukamel,et al.  Polarons, localization, and excitonic coherence in superradiance of biological antenna complexes , 1997 .

[46]  V. Sundström,et al.  Pump–probe spectroscopy of dissipative energy transfer dynamics in photosynthetic antenna complexes: A density matrix approach , 1997 .

[47]  G. Fleming,et al.  Quantum superpositions in photosynthetic light harvesting: delocalization and entanglement , 2010 .

[48]  Theoretical prediction of spectral and optical properties of bacteriochlorophylls in thermally disordered LH2 antenna complexes. , 2006, The Journal of chemical physics.

[49]  M. Schreiber,et al.  Reduced dynamics of coupled harmonic and anharmonic oscillators using higher-order perturbation theory. , 2007, The Journal of chemical physics.

[50]  Th. Förster.  Zwischenmolekulare Energiewanderung und Fluoreszenz , 1948 .

[51]  Arvi Freiberg,et al.  Excitonic polarons in quasi-one-dimensional LH1 and LH2 bacteriochlorophyll a antenna aggregates from photosynthetic bacteria : A wavelength-dependent selective spectroscopy study , 2009 .

[52]  Hohjai Lee,et al.  Coherence Dynamics in Photosynthesis: Protein Protection of Excitonic Coherence , 2007, Science.

[53]  Jan Amesz,et al.  Biophysical Techniques in Photosynthesis , 1996, Advances in Photosynthesis and Respiration.

[54]  Leonas Valkunas,et al.  Spectral dynamics of individual bacterial light-harvesting complexes: alternative disorder model. , 2008, Biophysical journal.

[55]  R. Kubo,et al.  Two-Time Correlation Functions of a System Coupled to a Heat Bath with a Gaussian-Markoffian Interaction , 1989 .

[56]  S. Mukamel,et al.  Exciton-migration and three-pulse femtosecond optical spectroscopies of photosynthetic antenna complexes , 1998 .

[57]  K. Schulten,et al.  Molecular Dynamics Methods for Bioelectronic Systems in Photosynthesis , 2008 .

[58]  Klaus Schulten,et al.  Energy transfer between carotenoids and bacteriochlorophylls in light-harvesting complex II of purple bacteria , 1999 .

[59]  Graham R Fleming,et al.  Exciton analysis in 2D electronic spectroscopy. , 2005, The journal of physical chemistry. B.

[60]  Hermann Haken,et al.  An exactly solvable model for coherent and incoherent exciton motion , 1973 .

[61]  Ladislav Nedbal,et al.  Photosynthesis in silico , 2009 .

[62]  Thomas Renger,et al.  Ultrafast excitation energy transfer dynamics in photosynthetic pigment–protein complexes , 2001 .

[63]  Arvi Freiberg,et al.  Excitons in core LH1 antenna complexes of photosynthetic bacteria: Evidence for strong resonant coupling and off-diagonal disorder , 2005 .

[64]  Klaus Schulten,et al.  Photosynthetic vesicle architecture and constraints on efficient energy harvesting. , 2010, Biophysical journal.

[65]  Volkhard May,et al.  Open system dynamics approach to polyatomic molecules : Excitons in chromophore complexes , 2006 .

[66]  V. Sundström,et al.  Energy transfer in the inhomogeneously broadened core antenna of purple bacteria: a simultaneous fit of low-intensity picosecond absorption and fluorescence kinetics. , 1994, Biophysical journal.

[67]  Arvi Freiberg,et al.  A disordered polaron model for polarized fluorescence excitation spectra of LH1 and LH2 bacteriochlorophyll antenna aggregates , 2006 .

[68]  Qiang Shi,et al.  Optical line shapes of molecular aggregates: hierarchical equations of motion method. , 2009, The Journal of chemical physics.

[69]  K. Sauer.  3 – Primary Events and the Trapping of Energy , 1972 .

[70]  K Schulten,et al.  Architecture and mechanism of the light-harvesting apparatus of purple bacteria. , 1998, Proceedings of the National Academy of Sciences of the United States of America.

[71]  G. Fleming,et al.  Quantum coherence and its interplay with protein environments in photosynthetic electronic energy transfer. , 2010, Physical chemistry chemical physics : PCCP.

[72]  Thomas Renger,et al.  On the relation of protein dynamics and exciton relaxation in pigment–protein complexes: An estimation of the spectral density and a theory for the calculation of optical spectra , 2002 .

[73]  A. Freiberg,et al.  Unraveling the Hidden Nature of Antenna Excitations , 2009 .