Spectral diffusion and drift: single chromophore and en masse.
Spectral diffusion and drift: single chromophore and en masse.
复制标题
光谱扩散和漂移：单个发色团和整体。
DOI：
--
复制
发表时间：
2007
影响因子：
4.4
通讯作者：
R. Silbey
中科院分区：
文献类型：
--
作者：
V. Lubchenko;R. Silbey
我们系统地描述了理想发色团与一般初始环境构型的非相干弛豫两态局域环境自由度（“自旋”）相互作用的光谱扩散。我们纠正了现有的不完整的处理方法，用适当的相关函数来表述问题，并获得了环境自旋的一般非周期排列的精确解，几乎不需要对多粒子自旋坐标分布的习惯简化假设。我们首次报道并估计了当窄谱线不在非均匀波段中心时产生的漂移和畸变的影响。虽然漂移在大多数系综测量中被证明是适度的，但在分析单个发色团光谱跳变时，考虑其影响是必不可少的，为此，作者提出了一个新的实验。此外，我们认为，通过采用足够大的生色团，可以将波动中心的浓度与其与生色团相互作用的强度解耦。最后，由于中心发色团频率的分布，对额外的线展宽进行了评估。对源自非平衡环境的类似展宽进行了上估计。
We develop a systematic description of spectral diffusion of ideal chromophores interacting with incoherently relaxing two-state, localized environmental degrees of freedom ("spins") for general initial environment configurations. We remedy the existing, incomplete treatments by formulating the problem in terms of the proper correlation function and by obtaining an accurate solution for generic aperiodic arrangements of environmental spins, nearly free of the customary simplifying assumptions on the multiparticle spin coordinate distribution. We report and estimate, for the first time, the effects of the drift and distortion of a narrow spectral line that arise when the line is not in the center of the inhomogeneous band. While the drift turns out to be modest in most ensemble measurements, accounting for its effects is imperative in analyzing single chromophore spectral jumps, to which end the authors propose a novel experiment. Further, we argue that by employing a sufficiently large chromophore one can decouple the concentration of the fluctuating centers from the strength of their interaction with the chromophore. Finally, the additional line broadening, owing to a distribution of the central chromophore frequencies, is evaluated. Upper estimates for an analogous broadening stemming from a nonequilibrium environment are made.