We revisit the line-shape theory of a single molecule with anomalous stochastic spectral diffusion. Waiting time profiles for bath induced spectral jumps in the ground and excited states become different when a molecule, probed by continuous-wave laser field, reaches the steady state. This effect is studied for the stationary dichotomic continuous-time-random-walk spectral diffusion of a single two-level chromophore with power-law distributions of waiting times. Correlated waiting time distributions, line shapes, two-point fluorescence correlation function, and Mandel Q parameter are calculated for arbitrary magnitude of laser field. We extended previous weak field results and examined the breakdown of the central limit theorem in photon statistics, indicated by asymptotic power-law growth of Mandel Q parameter. Frequency profile of the Mandel Q parameter identifies the peaks of spectrum, which are related to anomalous spectral diffusion dynamics.

Faculty of Mathematics and Physics Charles University Ke Karlovu 5 Prague 121 16 Czech Republic

References provided by Crossref.org

Center Line Slope Analysis in Two-Dimensional Electronic Spectroscopy