Sustainability of Environment‐Assisted Energy Transfer in Quantum Photobiological Complexes

It is shown that quantum sustainability is a universal phenomenon which emerges during environment‐assisted electronic excitation energy transfer (EET) in photobiological complexes (PBCs), such as photosynthetic reaction centers and centers of melanogenesis. We demonstrate that quantum photobiological systems must be sustainable for them to simultaneously endure continuous energy transfer and keep their internal structure from destruction or critical instability. These quantum effects occur due to the interaction of PBCs with their environment which can be described by means of the reduced density operator and effective non‐Hermitian Hamiltonian (NH). Sustainable NH models of EET predict the coherence beats, followed by the decrease of coherence down to a small, yet non‐zero value. This indicates that in sustainable PBCs, quantum effects survive on a much larger time scale than the energy relaxation of an exciton. We show that sustainable evolution significantly lowers the entropy of PBCs and improves the speed and capacity of EET.     

Correlated exciton relaxation in Poly(3-hexylthiophene)

Two-color 3 pulse photon echo peak shift (2C-3PEPS) measurements on poly(3-hexylthiophene) (3PHT) demonstrate that spectral regions in the photoluminescence remain correlated with the excitation, despite large differences in energy (>0.5 eV). The observations are explained in terms of exciton-phonon coupling that is dominated by only two motions: one high frequency bond stretch and a low frequency torsional motion. Numerical simulations of the 2C-3PEPS are shown to be consistent with the experimental observations. The results demonstrate that initial intramolecular exciton relaxation in P3HT is not primarily a stochastic process, but is driven by strong, selective exciton-phonon coupling to torsional motions.     

硝基甲烷振动能量弛豫的集体模型

用分子动力学方法结合Dlott等人提出的"门槛模"理论研究集体相互作用下硝基甲烷振动能量弛豫过程.其中振动冷却过程与实验符合的很好.在振动激发过程的分子动力学模拟中观测到与实验一致的基频频移现象.用分子动力学方法从微观上详细地描述出分子"门槛模"振动激发过程.研究表明,在高温高压作用下,集体作用效应对多原子振动激发具有不可忽视的作用,能量传递过程中除了基频的作用外,强烈的非线性相互作用引起的振动模泛频也携带有大量的振动能,这些泛频也对分子振动能量传递产生重要影响.     

Perfect quantum excitation energy transport via single edge perturbation in a complete network

We consider quantum excitation energy transport (EET) in a network of two-state nodes in the Markovian approximation by employing the Lindblad formulation. We find that EET from an initial site, where the excitation is inserted to the sink, is generally inefficient due to the inhibition of transport by localization of the excitation wave packet in a symmetric, fully-connected network. We demonstrate that the EET efficiency can be significantly increased up to ≈100% by perturbing hopping transport between the initial node and the one connected directly to the sink, while the rate of energy transport is highest at a finite value of the hopping parameter. We also show that prohibiting hopping between the other nodes which are not directly linked to the sink does not improve the efficiency. We show that external dephasing noise in the network plays a constructive role for EET in the presence of localization in the network, while in the absence of localization it reduces the efficiency of EET. We also consider the influence of off-diagonal disorder in the hopping parameters of the network.     

Theoretical study on the exciton dynamics of coherent excitation energy transfer in the phycoerythrin 545 light-harvesting complex

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.     

Effects of confinement on the electron and lattice dynamics in metal nanoparticles

Effects of confinement on the electron-electron (e-e) and electron-phonon (e-ph) thermalization dynamics in noble metal clusters are calculated using simple approaches. The model predictions are compared with femtosecond pump-probe measurements which display an acceleration of the e-e and e-ph relaxation dynamics. The size-effects on the e-e relaxation dynamics are consistent with a model involving the surface-induced reduction of the screening efficiency of the Coulomb e-e interaction. With regard to the e-ph relaxation dynamics, this model yields too large time constants, pointing out deficiencies of the standard modelling of the e-ph energy exchanges in bulk metals. Analysis of these deficiencies shows that the bare e-ion interaction has to be involved in the transition matrix element describing the non-adiabatic e-ph energy exchanges.     

Excitonic relaxation in a conjugated polymer: Initial coherence beyond energy-dispersive population transfer

In this contribution, we deal with the pathways of femtosecond excitonic relaxation in conjugated polymers, focusing on the prominent, ground-state nondegenerate model system poly(p-phenylenevinylene) (PPV). After a brief discussion of the molecular exciton picture of optical excitations in organic semiconductors, we present exemplary results, categorized in two regimes. On early picosecond time scales, the dynamics of incoherent population relaxation is investigated by combining selectively tuned femtosecond excitation pulses with the technique of fluorescence up-conversion. As an initially prepared excitonic distribution gradually lowers its energy by diffusion to the bottom of the density of states (DOS), an excitation energy-dependent bathochromic shift dynamics is observed, accompanied by spectral intensity rearrangements. Motivated by the perception that intersite electronic coupling is absent in the lowest energy regime of the DOS, we further devise a strategy that enables us to measure the very early electronic oscillations and their quantum-stochastic relaxation within approximately the first 200 fs. By using femtosecond wave packet interferometry with appropriately tuned but otherwise freely propagating pulses, we observe fluorescence interferograms with strongly damped, low-frequency beatings, which stem from the spatial interference of two wave packets launched by two-pulse excitation. The results can be explained, semiquantitatively, in terms of a second-order perturbational approach and open up a new perspective on the complex puzzle of PPV optical dynamics.     

Light absorption and excitation energy transfer calculations in primitive photosynthetic bacteria

In photosynthetic organisms, light energy is converted into chemical energy through the light absorption and excitation energy transfer (EET) processes. These processes start in light-harvesting complexes, which contain special photosynthetic pigments. The exploration of unique mechanisms in light-harvesting complexes is directly related to studies, such as artificial photosynthesis or biosignatures in astrobiology. We examined, through ab initio calculations, the light absorption and EET processes using cluster models of light-harvesting complexes in purple bacteria (LH2). We evaluated absorption spectra and energy transfer rates using the LH2 monomer and dimer models to reproduce experimental results. After the calibration tests, a LH2 aggregation model, composed of 7 or 19 LH2s aligned in triangle lattice, was examined. We found that the light absorption is red shifted and the energy transfer becomes faster as the system size increases. We also found that EET is accelerated by exchanging the central pigments to lower energy excited pigments. As an astrobiological application, we calculated light absorptions efficiencies of the LH2 in different photoenvironments.     

NMR relaxation study of molecular dynamics in columnar and smectic phases of a PAMAM liquid-crystalline co-dendrimer

We present the first results obtained by proton (¹H) nuclear magnetic relaxation studies of molecular dynamics in a supermolecular liquid-crystal dendrimer exhibiting columnar rectangular and smectic-A phases. The ¹H spin-lattice relaxation time (T₁) dispersions are interpreted using two relaxation mechanisms associated with collective motions and local molecular reorientations of the dendritic segments in the low- and high-frequency ranges, respectively. The T₁ values show a drop around 2.3 MHz that is attributed to a contribution coming from cross-relaxation between ¹H and nitrogen nuclear spins. In the high-frequency range the motions appear to be of similar nature in both mesophases and are ascribed to reorientations of dendritic segments (belonging to the core and/or to the mesogenic units) characterized by two correlation times. Notable differences in the dynamics between the columnar and layered phases are observed in the low-frequency range. Depending on the mesophase they are discussed in terms of elastic deformations of the columns and layer undulations. In this study we find that the dendritic core influences the dynamics of the mesogenic units both for local and collective motions. These results can be understood in terms of spatial constraints imposed by the dendritic architecture and by the supermolecular arrangement in the mesophases.     

Geometry Relaxation of Photoexcited States in Conjugated Molecules

The random phase approximation combined with semiempirical Hamiltonians is applied to compute and analyze electronic structure and excited state adiabatic potentials of several conjugated molecules. Calculated excited state energies and parameters of molecular adiabatic surfaces characterize the coupled dynamics of vibrational and electronic degrees of freedom. The analysis identifies the specific torsional and bond-stretching nuclear motions that dominate the excited state relaxation and lead to self-localized excitations. This approach is an inexpensive and numerically efficient method of computing molecular excited state adiabatic surfaces and modeling femto-to-pico second time-dependent photoexcitation processes along chosen trajectories.     

Time-resolved torsional relaxation of spider draglines by an optical technique

The sensitivity of the torsional pendulum demonstrates the self-shape-memory effect in different types of spider draglines. Here we report the time-resolved noncovalent bonds recovery in the protein structure. The torsional dynamics of such multilevel structure governed by reversible interactions are described in the frame of a nested model. Measurement of three different relaxation times confirms the existence of three energy storage levels in such two protein spidroin systems. Torsion opens the way to further investigations towards unraveling the tiny torque effects in biological molecules.     

Magnetic density of states at low energy in geometrically frustrated systems

Using muon-spin-relaxation measurements we show that the pyrochlore compound Gd(2)Ti(2)O(7), in its magnetically ordered phase below approximately 1 K, displays persistent spin dynamics down to temperatures as low as 20 mK. The characteristics of the induced muon relaxation can be accounted for by a scattering process involving two magnetic excitations, with a density of states characterized by an upturn at low energy and a small gap depending linearly on the temperature. We propose that such a density of states is a generic feature of geometrically frustrated magnetic materials.     

Probing slow dynamics in supported thin polymer films

We have used variable cooling rate ellipsometric measurements to probe the slow dynamics in thin supported polystyrene films. For the slowest cooling rates (approximately 1 K/min) the measured Tg values are reduced below the bulk value with the measured Tg of 341 K for a 6 nm film. As the cooling rate is increased the Tg reductions become smaller until at cooling rates >90 K/min there is only slight evidence for a film-thickness-dependent Tg value. By relating the cooling rate to a relaxation time, we show that the relaxation dynamics of the thin films appears to become Arrhenius with an activation energy that decreases with decreasing film thickness. We discuss this in terms of a possible connection to a length scale for cooperative motion. Finally, the results can be used to resolve a number of outstanding contradictory reports in the literature.     

高等植物外周捕光天线LHCⅡ中的超快光动力学过程

利用飞秒抽运探测技术及时间分辨荧光(TRPL)等光谱技术对高等植物LHCⅡ中的超快光动力学过程进行了研究。在其时间分辨荧光光谱中表现出了明显的各向异性特性。实验上观察了LHCⅡ中色素间的能量传递过程,由飞秒动力学发现,单体内Chlb到邻近的Chla之间的能量传递在200～300fs的时间尺度,Chla激子带间的能量弛豫发生在几百飞秒,不同单体Chla分子间能量分布过程在几个皮秒。而时间分辨荧光和飞秒动力学过程中上百皮秒的慢过程归属于不同聚集体间的能量平衡过程或分子构象变化。     

基于分子束外延生长的1.05 eV InGaAsP的超快光学特性研究

利用分子束外延方法制备了应用于四结光伏电池的1.05 eV InGaAsP薄膜, 并对其超快光学特性进行了研究. 温度和激发功率有关的发光特性表明: InGaAsP材料以自由激子发光为主. 室温下InGaAsP材料的载流子发光弛豫时间达到10.4 ns, 且随激发功率增大而增大. 发光弛豫时间随温度升高呈现S形变化, 在低于50 K时随温度升高而增大, 在50–150 K之间时减小, 而温度高于150 K时再次增大. 基于载流子弛豫动力学, 分析并解释了温度及非辐射复合中心浓度对样品材料载流子发光弛豫时间S形变化的影响.     

Probing chromosome structure with dynamic force relaxation

We report measurements of the dynamics of force relaxation in single mitotic chromosomes, following step strains applied with micropipettes of force constant approximately 1 nN/microm. The force relaxes exponentially after an elongation (l/l(0)) to less than 3x native length, with a relaxation time approximately 2 sec. This relaxation time corresponds to an effective viscosity approximately 10(5) times that of water. We experimentally rule out solvent flow into the chromosome as the mechanism for the relaxation time. Instead, the relaxation can be explained in terms of the disentanglement dynamics of approximately 80 kb chromatin loop domains.     

Polarization-dependent carrier dynamics in a passive InAs/InP quantum dot waveguide

We investigate carrier dynamics in a passive InAs/InP quantum dot (QD) waveguide using 255 fs optical pulses at a central wavelength of 1568 nm. We observe strong anisotropy of absorption saturation for different polarizations. Pump-probe measurements indicate the presence of carrier relaxation dynamics on a timescale in the order of tens of picoseconds due to cascaded relaxation of carriers generated by two-photon absorption (TPA) from the bulk region to the QDs via the wetting layer. These relaxation timescales are much longer than in QD amplifiers. Our observations are supported by a rate-equation model which includes TPA, showing good agreement with the pump-probe measurements.     

共轭聚合物单分子构象和能量转移特性研究

利用基于宽场显微光学系统的单分子散焦成像技术测量了不同构象poly[2,7-(9,9-dioctylfluorene)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole](PFO-DBT)共轭聚合物单分子的光物理与动力学特性.通过分析共轭聚合物单分子的荧光轨迹和对应的发射偶极取向变化识别共轭聚合物单分子发光单元,发现延伸构象下的单分子呈现多发色团发光特性,而折叠构象下的单分子保持高效链间能量转移,呈现单个发色团发光特性.共轭聚合物单分子构象对能量转移效率的影响可用于研究基于共轭聚合物的光电器件和分子器件.