On the relation between the echo-peak shift and Brownian-oscillator correlation function

We show that for systems that exhibit bimodal dynamics in their system-bath correlation function the shift of the stimulated photon-echo maximum as a function of waiting time reflects fairly well the long time part of the correlation function. For early times this correspondence breaks down due to a fundamentally different behaviour of the echo-peak shift in this time domain and because of the effect of finite pulse duration on the echo-peak shift. The method is used to characterize the solvation dynamics in various dye solutions.

The Energy Landscape of Myoglobin: An Optical Study

In this paper we demonstrate how the potential energy surface of a protein, which determines its conformational degrees of freedom, can be constructed from a series of advanced nonlinear optical experiments. The energy landscape of myoglobin was probed by studying its low-temperature structural dynamics, using several spectral hole burning and photon echo techniques. The spectral diffusion of the heme group of the protein was studied on a time scale ranging from nanoseconds to several days while covering a temperature range from 100 mK to 23 K. The spectral line broadening, as measured in three-pulse stimulated photon echo experiments, occurs in a stepwise fashion, while the exact time dependence of the line width is critically dependent on temperature. From these results we obtained the energy barriers between the conformational states of the protein. Aging time dependent hole-burning experiments show that, at 100 mK, it takes several days for the protein to reach thermal equilibrium. When, after this period a spectral hole is burned, the line broadening induced by well-defined temperature cycles is partly reversed over a period of several hours. From this we conclude that a rough structure is superimposed on the overall shape of the potential energy surface of the protein. By combining the hole burning and photon echo results, we construct a detailed image of this energy landscape, supporting the general concept of a structural hierarchy. More specifically, we show that the number of conformational substates in the lower hierarchical tiers is much lower than was previously anticipated and, in fact, is comparable to the number of taxonomic substates.

Photon echoes stimulated from an accumulated grating:Theory of generation and detection

We present a theoretical description of the generation and detection of photon echoes, stimulated from an accumulated frequency grating in the inhomogeneous distribution. We show that detection of the echoes takes place via interference in the sample between a properly phased and directed probe pulse and the echo polarization. In this description the echo phenomenon emerges as an induced transparency of the sample rather than a burst of coherent radiation. By solving simultaneously the optical Bloch and Maxwell equations, an expression is obtained which correlates quantitatively the echo intensity to the decay parameters, pulse intensity, and the transition moment. As an application of the theory we present results on the intersystem crossing of pentacene in naphthalene at 1.5 K

Vibronic relaxation in molecular mixed crystals:Pentacene in naphthalene and p-terphenyl

Picosecond photon echo techniques are used to measure directly vibronic relaxation times in the first excited singlet state of pentacene in naphthalene and p-terphenyl. In regions of low (< 300 cm–1) and high (> 1000 cm–1) vibrational energy, relaxation is fast (τ <2 ps) due to direct phonon emission (low energy) and fast vibrational energy redistribution (high energy). In the intermediate region relaxation times vary drastically. Effects of isotope substitution of guest and host suggest intramolecular relaxation in this region. Changes in local environment are shown to influence the relaxation rate quite drastically, indicating large host-induced anharmonic coupling between different vibrations

Spectroscopy of Chemically Linked Dimers:1,3-(1,1’-Dinaphthyl)propane in a Naphthalene Host

Results of absorption, fluorescence and selective-excitation experiments on the chemically linked dimer 1,3-(1,1'-dinaphthyl)propane in a naphthalene host at 1.8 K are presented. This system is shown to consist of two translationally inequivalent pairs of the naphthalene moiety, occupying non-substitutional sites in the host lattice. This gives rise to two sets of dimer absorptions, split by 40 and 97 cm -1

Observation of the one-exciton to two-exciton transition in a J aggregate

We report on the first observation of the one-exciton to two-exciton transition in J aggregates. A theoretical analysis supports our interpretation

Dynamics of Frenkel excitons in disordered molecular aggregates

This article reports on the optical dynamics in aggregates of pseudoisocyanine-bromide and iodide. For PIC-Br in an ethylene glycol/water glass, the results of resonance light scattering (RLS), time-resolved emission, and photon echo decay measurements are discussed. Band structure calculations based on a linear-chain model for the J aggregate have also been performed. The results show that the J band can be described as a disordered Frenkel exciton band in which superradiant states exist that extend over about 100 molecules. Numerical simulation studies of the J band, based on Anderson's Hamiltonian with uncorrelated diagonal site energies, show that the ratio kappa of the disorder parameter D over the nearest-neighbor coupling parameter J12 is about 0.11. Using the frequency dependence of the ratio between the yields of vibrational fluorescence and Raman scattering as a probe, the dephasing process and derived parameters for the bath correlation function at three different temperatures have also been examined. It is shown that at all temperatures the exciton dephasing process occurs in the fast modulation limit. For PIC-I in a Langmuir-Blodgett film the optical excitation can be described also in terms of a band transition but the disorder is much larger than in a glass. For this system, a low-temperature fluorescence lifetime of about 10 ps is measured, which suggests that the excitation is much more delocalized than in the case of self-assembled aggregates in a glass. Resonance Rayleigh scattering experiments on PIC in a bilayer show that the exciton-dephasing rate increases dramatically at energies above the renormalized band edge