Role of quantum coherence in shaping the line shape of an exciton interacting with a spatially and temporally correlated bath

摘要

Kubo’s fluctuation theory of line shape forms the backbone of our understanding of optical and vibrational line shapes, through such concepts as static heterogeneity and motional narrowing. However, the theory does not properly address the effects of quantum coherences on optical line shape, especially in extended systems where a large number of eigenstates are present. In this work, we study the line shape of an exciton in a one-dimensional lattice consisting of regularly placed and equally separated optical two level systems. We consider both linear array and cyclic ring systems of different sizes. Detailed analytical calculations of line shape have been carried out by using Kubo’s stochastic Liouville equation (SLE). We make use of the observation that in the site representation, the Hamiltonian of our system with constant off-diagonal coupling J is a tridiagonal Toeplitz matrix (TDTM) whose eigenvalues and eigenfunctions are known analytically. This identification is particularly useful for long chains where the eigenvalues of TDTM help understanding crossover between static and fast modulation limits. We summarize the new results as follows. (i) In the slow modulation limit when the bath correlation time is large, the effects of spatial correlation are not negligible. Here the line shape is broadened and the number of peaks increases beyond the ones obtained from TDTM (constant off-diagonal coupling element J and no fluctuation). (ii) However, in the fast modulation limit when the bath correlation time is small, the spatial correlation is less important. In this limit, the line shape shows motional narrowing with peaks at the values predicted by TDTM (constant J and no fluctuation). (iii) Importantly, we find that the line shape can capture that quantum coherence affects in the two limits differently. (iv) In addition to linear chains of two level systems, we also consider a cyclic tetramer. The cyclic polymers can be designed for experimental verification. (v) We also build a connection between line shape and population transfer dynamics. In the fast modulation limit, both the line shape and the population relaxation, for both correlated and uncorrelated bath, show similar behavior. However, in slow modulation limit, they show profoundly different behavior. (vi) This study explains the unique role of the rate of fluctuation (inverse of the bath correlation time) in the sustenance and propagation of coherence. We also examine the effects of off-diagonal fluctuation in spectral line shape. Finally, we use Tanimura-Kubo formalism to derive a set of coupled equations to include temperature effects (partly neglected in the SLE employed here) and effects of vibrational mode in energy transfer dynamics.