Dutta Rajesh, Bagchi Biman
SSCU, Indian Institute of Science, Bangalore 560012, India.
J Phys Chem B. 2020 Jun 4;124(22):4551-4563. doi: 10.1021/acs.jpcb.0c02190. Epub 2020 May 24.
Quantum coherence controls almost every aspect of static and dynamic response of a strongly correlated quantum system, although details of this control have not been elucidated in many cases. We find that, in the presence of a significant static off-diagonal coupling, quantum coherence can survive much longer than the bath correlation time in a noisy environment. In the presence of time correlated noise (non-Markovian limit), coherence could propagate through the excited bath states, and this plays a nontrivial role in giving rise to a noncanonical temperature dependence of population distribution in an extended conjugated polymer-like system. The quantum coherence through the excited bath states vanishes in the high temperature limit, giving rise to the equilibrium Boltzmann distribution. Second, we discuss a role of quantum coherence in exciton localization that bears resemblance to Anderson localization. Calculations have been carried out not only with a chain of conjugated polymer but also with dimer and trimer subunits of the Fenna-Matthews-Olson (FMO) complex. We derive an analytical expression of the relation between steady state coherence and excitionic population distribution. We analytically showed that steady state coherence in equilibrium bath states is governed by interchromophoric coupling () whereas coherence in excited bath states is dictated by fluctuation strength () for the spatially correlated bath model. For the spatially uncorrelated bath model, we observe that at the low temperature limit coherence in the excited bath states dominates over coherence in equilibrium bath states and vice versa. In the study of the localization problem, we analytically show that, in the limit of a negligibly small fluctuation rate (), the diffusion coefficient is exactly proportional to the fluctuation rate, leading to complete breakdown of the Haken-Strobl-Silbey Markovian prediction.
量子相干控制着强关联量子系统静态和动态响应的几乎每个方面,尽管在许多情况下这种控制的细节尚未阐明。我们发现,在存在显著静态非对角耦合的情况下,量子相干在噪声环境中的存活时间可比热库关联时间长得多。在存在时间关联噪声(非马尔可夫极限)的情况下,相干可以通过激发的热库态传播,这在扩展的类共轭聚合物系统中产生非规范的布居分布温度依赖性方面起着重要作用。通过激发热库态的量子相干在高温极限下消失,从而产生平衡玻尔兹曼分布。其次,我们讨论了量子相干在与安德森局域化相似的激子局域化中的作用。不仅对共轭聚合物链,而且对费纳 - 马修斯 - 奥尔森(FMO)复合物的二聚体和三聚体亚基都进行了计算。我们推导了稳态相干与激子布居分布之间关系的解析表达式。我们通过解析表明,对于空间相关热库模型,平衡热库态中的稳态相干由发色团间耦合()决定,而激发热库态中的相干由涨落强度()决定。对于空间不相关热库模型,我们观察到在低温极限下,激发热库态中的相干主导平衡热库态中的相干,反之亦然。在局域化问题的研究中,我们通过解析表明,在涨落率可忽略不计的极限()下,扩散系数与涨落率精确成正比,导致哈肯 - 施特罗布尔 - 西尔贝马尔可夫预测完全失效。