Abstract
By using laser FM spectroscopy, we have observed statistical fine structure (SFS) in the inhomogeneously broadened zero‐phonon S1←S0 (0–0) absorption of pentacene molecules in crystals of p‐terphenyl at liquid helium temperatures. SFS results from variations in the spectral density of absorbers with optical wavelength due to statistics, illustrating that the inhomogeneous line profile is not a simple, smooth Gaussian function as has been previously assumed but rather contains significant fine structure. Theoretical analysis of the SFS spectra using autocorrelation techniques can be used to estimate the underlying value of the homogeneous linewidth. This new observation not only provides a novel way to study the statistics of inhomogeneous broadening, but it also allows estimation of the homogeneous width without requiring spectral hole‐burning or coherent transient techniques.
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