Time-domain chirally-sensitive three-pulse coherent probes of vibrational excitons in proteins

Abramavičius, Darius; Mukamel, Shaul

doi:10.1016/j.chemphys.2005.06.046

Cited by 23 publications

(34 citation statements)

References 48 publications

(101 reference statements)

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“…Exciton scattering (Appendix E) is best described in the eigenstate basis 79,91,108. This leads to efficient truncation schemes of the scattering matrix, based on transition amplitudes and on the exciton-overlap integrals.…”

Section: Optical Response Of Quasiparticles With Relaxationmentioning

confidence: 99%

Coherent Multidimensional Optical Spectroscopy of Excitons in Molecular Aggregates; Quasiparticle versus Supermolecule Perspectives

et al. 2009

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Section: Optical Response Of Quasiparticles With Relaxationmentioning

confidence: 99%

Coherent Multidimensional Optical Spectroscopy of Excitons in Molecular Aggregates; Quasiparticle versus Supermolecule Perspectives

et al. 2009

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“…These are known as the nonlinear exciton equations (10,12,33,(37)(38)(39). In the singleexciton eigenstate representation of quasiparticle scattering, the response function for k III technique is (12,39,40): where I e () ϭ i( Ϫ e ϩ i␥) Ϫ1 and Ᏻ eeЈ () ϭ i( Ϫ e Ϫ eЈ ϩ 2i␥) Ϫ1 are the single-exciton and noninteracting double-exciton Green's functions, and ␥ is the dephasing rate.…”

Section: Quasiparticle-scattering Picture Of Double Excitations and Tmentioning

confidence: 99%

Double-quantum resonances and exciton-scattering in coherent 2D spectroscopy of photosynthetic complexes

Abramavičius

Voronine

Mukamel

2008

Proc. Natl. Acad. Sci. U.S.A.

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A simulation study demonstrates how the nonlinear optical response of the Fenna-Matthews-Olson photosynthetic light-harvesting complex may be explored by a sequence of laser pulses specifically designed to probe the correlated dynamics of double excitations. Cross peaks in the 2D correlation plots of the spectra reveal projections of the double-exciton wavefunctions onto a basis of direct products of single excitons. An alternative physical interpretation of these signals in terms of quasiparticle scattering is developed.exciton transport ͉ femtosecond spectroscopy ͉ photosynthesis ͉ light harvesting T he photosynthetic apparatus depends on light-harvesting complexes, which absorb photons and funnel their energy to reaction centers where it is converted and stored as chemical energy (1, 2). The Fenna-Matthews-Olson (FMO) complex is the prototype photosynthetic antenna (3, 4). The complex (Fig. 1) is a trimer of identical units, each containing seven chlorophyll a chromophores embedded in the protein matrix. The structure and properties of the complex have been studied extensively over the past decade (3-7).Electronically excited FMO complexes prepared by the absorption of a single photon are well understood, and their properties are described by the Frenkel exciton model (2,8,9). The elaborate exciton-relaxation pattern can be monitored by using multidimensional coherent optical spectroscopy (10-12): peak redistribution on the picosecond time scale reflects excited-state population relaxation (7), whereas femtosecond oscillations indicate electronic coherences (13). Excited-state lifetimes, intraband excitonrelaxation pathways (7,14), and long-lived electronic quantum coherences (13) have been reported, and the Hamiltonian parameters were refined to simulate these measurements.In the native environment, under the intense flux of sunlight, photosynthetic complexes have multiple electronic excitations, the interactions of which cause dissipation of the excess energy (1, 2, 9, 15, 16). Biological complexes have developed various protective mechanisms for excess energy discharge to avoid overheating and damage (17,18). Understanding the coherent many-exciton dynamics, which precedes the incoherent relaxation, is necessary for revealing the initial steps in excitation dynamics. Information about the two-exciton manifold is also important for the applications of the coherent control of excitedstate dynamics of photosynthetic complexes (19). Doubleexciton resonances are much more complicated and less studied than the single excitations. Exciton annihilation, which depends on incoherent multiexciton dynamical properties, often complicates the analysis of nonlinear optical measurements.In this article we present simulations of an impulsive thirdorder 2D coherent spectroscopic (2DCS) technique aimed at directly probing double-exciton features in an FMO complex. In most commonly used four-wave-mixing techniques, such as pump-probe, three-pulse peak shift and photon echo, doubleexciton information is convoluted with single...

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“…The electronic excitations are described using the Frenkel exciton model [22]. The chromophore excitation energy is E 0 .…”

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“…The homogeneous signal is then given in terms of single-exciton eigenstates with energies ε e and transition dipoles d e at κ = 0, and the exciton scattering matrix Γ [22]:

\begin{matrix} left \\ S_{h} false(ω_{3}, ω_{2} false) & = & ℑ \sum_{ijkl} \frac{〈 d_{l} d_{k} d_{j} d_{i} 〉}{false(ω_{3} - ξ_{l} false) false(ω_{2} - ω_{3} - ξ_{k}^{*} false)} \\ \times [\frac{Γ_{italiclk, italicji} false(ω_{3} + ξ_{k}^{*} false)}{ω_{3} + ξ_{k}^{*} - ξ_{i} - ξ_{j}} - \frac{Γ_{italiclk, italicji} false(ω_{2} false)}{ω_{2} - ξ_{i} - ξ_{j}}], \end{matrix}

where ijkl runs over e 1 - e 3 , 〈 d l d k d j d i 〉 is the orientationally averaged product of their transition dipoles, ξ j = ε j − iγ j , where γ j is the dephasing rate of exciton j . Γ lk,ji can be numerically calculated for a periodic system as described in Appendix F of Ref.…”

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Weak Exciton Scattering in Molecular Nanotubes Revealed by Double-Quantum Two-Dimensional Electronic Spectroscopy

et al. 2012

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The two-exciton manifold of a double-wall cylindrical molecular aggregate is studied using a coherent third order optical technique. Experiments reveal the anharmonic character of the exciton bands. Atomistic simulations of the exciton-exciton scattering show that the excitons can be treated as weakly coupled hard-core bosons. The weak coupling stems from the extended exciton delocalization made possible by the nanotube geometry.

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Time-domain chirally-sensitive three-pulse coherent probes of vibrational excitons in proteins

Cited by 23 publications

References 48 publications

Coherent Multidimensional Optical Spectroscopy of Excitons in Molecular Aggregates; Quasiparticle versus Supermolecule Perspectives

Coherent Multidimensional Optical Spectroscopy of Excitons in Molecular Aggregates; Quasiparticle versus Supermolecule Perspectives

Double-quantum resonances and exciton-scattering in coherent 2D spectroscopy of photosynthetic complexes

Weak Exciton Scattering in Molecular Nanotubes Revealed by Double-Quantum Two-Dimensional Electronic Spectroscopy

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