Department of Physics and Astronomy and Center for Quantum Information Science and Technology, University of Southern California, Los Angeles, CA 90089-0484, USA.
Philos Trans A Math Phys Eng Sci. 2012 Aug 13;370(1972):3750-70. doi: 10.1098/rsta.2011.0213.
Symmetric couplings among aggregates of n chromophores increase the transfer rate of excitons by a factor n(2), a quantum-mechanical phenomenon called 'supertransfer'. In this work, we demonstrate how supertransfer effects induced by geometrical symmetries can enhance the exciton diffusion length by a factor n along cylindrically symmetric structures, consisting of arrays of rings of chromophores, and along spiral arrays. We analyse both closed-system dynamics and open quantum dynamics, modelled by combining a random bosonic bath with static disorder. In the closed-system case, we use the symmetries of the system within a short-time approximation to obtain a closed analytical expression for the diffusion length that explicitly reveals the supertransfer contribution. When subject to disorder, we show that supertransfer can enhance excitonic diffusion lengths for small disorders and characterize the crossover from coherent to incoherent motion. Owing to the quasi-one-dimensional nature of the model, disorder ultimately localizes the excitons, diminishing but not destroying the effects of supertransfer. When dephasing effects are included, we study the scaling of diffusion with both time and number of chromophores and observe that the transition from a coherent, ballistic regime to an incoherent, random-walk regime occurs at the same point as the change from supertransfer to classical scaling.
对称耦合的 n 个发色团聚集体通过因子 n(2)增加激子的转移速率,这是一种被称为“超转移”的量子力学现象。在这项工作中,我们展示了由几何对称性引起的超转移效应如何沿着圆柱对称结构(由发色团环的阵列和螺旋阵列组成)将激子扩散长度增强 n 倍。我们分析了封闭系统动力学和开放量子动力学,通过将随机玻色子浴与静态无序相结合来建模。在封闭系统的情况下,我们在短时间近似内利用系统的对称性来获得扩散长度的封闭解析表达式,该表达式明确揭示了超转移的贡献。当受到无序影响时,我们表明,在小无序的情况下,超转移可以增强激子的扩散长度,并描述从相干到非相干运动的转变。由于模型的准一维性质,无序最终使激子局域化,削弱但不会破坏超转移的影响。当包括退相效应时,我们研究了扩散与时间和发色团数量的标度关系,并观察到从相干、弹道态到非相干、随机漫步态的转变与从超转移到经典标度的转变发生在同一时刻。