The mean-size dependence of the exchange narrowing in molecular J-aggregates

The effect of segment-size fluctuations on exchange narrowing in a molecular J-aggregate of site-energy disordered distributions is studied using a one-dimensional Frenkel-exciton model. It is found that the segment-size disorder leads to the width of the absorption spectra deviating from the scaling law, σ4/3 of the site-energy disordered standard deviation σ, being suitable for the system only with the site-energy disorder. In larger σ, the segment-size disorder has little influence on the linear absorption spectra. With increasing segment mean-length, the absorption line width monotonically increases, and then approaches a saturated value. By comparing a system of larger mean-length segment with a smaller one, both with the same segment-size disorder, it is found that the absorption line width of the former is broadened, and the exchange narrowing effect is reduced. The present result shows that the correlation effect can be partially maintained for the system with larger mean-length segment.

Research Highlights
► Segment fluctuations affect the exchange narrowing of molecular J-aggregates.
► The width of the absorption spectra is found to deviate from the scaling law.
► Increase in segment size causes increase in the width and then saturates.
► Exchange narrowing is reduced for larger mean-size segment.
► Correlation can be kept partly in the larger size segment.