Photoisomerization dynamics of a light-driven molecular rotary motor, 9-(2-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ylidene)-9H-fluorene, is investigated with trajectory surface-hopping dynamics at the semiempirical OM2/MRCI level. The rapid population decay of the S excited state for the M isomer is observed, with two different decay time scales (500 fs and 1.0 ps). By weighting the contributions of fast and slow decay trajectories, the averaged lifetime of the S excited state is about 710 fs. The calculated quantum yield of the M-to-P photoisomerization of this molecular rotary motor is about 59.9%. After the S → S excitation, the dynamical process of electronic decay is followed by twisting about the central C═C double bond and the motion of pyramidalization at the carbon atom of the stator-axle linkage. Although two S/S minimum-energy conical intersections are obtained at the OM2/MRCI level, only one conical intersection is found to be responsible for the nonadiabatic dynamics. The existence of "dark state" in the molecular rotary motor is confirmed through the simulated time-resolved fluorescence emission spectrum. Both quenching and red shift of fluorescence emission spectrum observed by Conyard et al. [ Conyard, J.; Addison, K.; Heisler, I. A.; Cnossen, A.; Browne, W. R.; Feringa, B. L.; Meech, S. R. Nat. Chem. 2012 , 4 , 547 - 551 ; Conyard, J.; Conssen, A.; Browne, W. R.; Feringa, B. L.; Meech, S. R. J. Am. Chem. Soc. 2014 , 136 , 9692 - 9700 ] are well understood. We find that this "dark state" in the molecular rotary motor is not a new electronic state, but the "dark region" with low oscillator strength on the initial S state.
In recent years, two-dimensional (2D) electronic spectroscopy experiments prove that the excitation energy transfer (EET) in photosynthetic light-harvesting systems presents long-lived electronic quantum beating signals. After being discovered in the light-harvesting system, the quantum coherence effect has aroused widespread discussion. To illustrate the EET process in the Fenna–Matthews–Olson (FMO) and phycocyanin 645 (PC645) complex, the local protein environment is often thought to be the same; however, this is ambivalent to the practical structural analysis of the light-harvesting complex. By adopting the dissipaton equation of motion theory, we present the effect of a heterogeneous protein environment on the energy transfer process with accurate numerical results. We demonstrate that the energy transfer process relies on the local heterogeneous environment for the FMO complex. A similar good agreement is found for the PC645 complex. Furthermore, we discuss the optimal value of different chromophores in the excitation energy transfer process by controlling the environmental characteristics.
The role of pigment–protein coupling in the dynamics of photosynthetic energy transport in chromophoric complexes has not been fully understood. The excitation energy transfer in the photosynthetic system is tremendously efficient. In particular, we investigate the excitation energy transport in the Fenna–Matthews–Olson (FMO) complex. The exciton dynamics and excitation energy transfer (EET) depend on the interaction between the excited chromophores and their environment. Most theoretical models believe that all bacteriochlorophyll-a (BChla) sites are surrounded by the same local protein environment, which is contradicted by the structural analysis of the FMO complex. Based on different values of pigment–protein coupling for different sites, measured in the adiabatic limit, we have theoretically investigated the effect of the heterogeneous local protein environment on the EET process. By the realistic and site-dependent model of the system–bath couplings, the results show that this interaction may have a critical value for the coherent energy-transfer process. Furthermore, we verify that the two transport pathways are coherent and stable to the important parameter reorganization energy of environmental interactions. The quantum dynamical simulations show that the correlation fluctuation keeps the oscillation of the coherent excitation on a long timescale. In addition, due to the inhomogeneous pigment–protein coupling, different BChl sites have asymmetric excitation oscillation timescales.
The experimental observation of long-lived quantum coherence in the excitation energy transfer (EET) process of the several photosynthetic light-harvesting complexes at low and room temperatures has aroused hot debate. It challenges the common perception in the field of complicated pigment molecular systems and evokes considerable theoretical efforts to seek reasonable explanations. In this work, we investigate the coherent exciton dynamics of the phycoerythrin 545 (PE545) complex. We use the dissipation equation of motion to theoretically investigate the effect of the local pigment vibrations on the population transfer process. The result indicates that the realistic local pigment vibrations do assist the energy transmission. We demonstrate the coherence between different pigment molecules in the PE545 system is an essential ingredient in the EET process among various sites. The coherence makes the excitation energy delocalized, which leads to the redistribution of the excitation among all the chromophores in the steady state. Furthermore, we investigate the effects of the complex high-frequency spectral density function on the exciton dynamics and find that the high-frequency Brownian oscillator model contributes most to the exciton dynamic process. The discussions on the local pigment vibrations of the Brownian oscillator model suggest that the local heterogeneous protein environments and the effects of active vibration modes play a significant role in coherent energy transport.
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