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.
A theory of optical echo spectroscopies of large polyatomic molecules in condensed phases is developed. Using phase space correlation functions, we examine the interrelationships among the following optical measurements: ordinary photon echo, stimulated photon echo, accumulated photon echo, incoherent accumulated photon echo, and pump–probe absorption. Conditions for the elimination of inhomogeneous broadening in these experiments are specified. A multimode Brownian oscillator model is used to account for high frequency molecular vibrations, as well as solvent modes, and electronic dephasing processes. The effects of quantum beats, spectral diffusion, and homogeneous dephasing on the echo signals are studied and compared in detail with pump–probe and hole burning spectroscopy.
Accumulated photon echoes (APE) were used to measure the dephasing rates of Nd3+ in various inorganic glasses as a function of excitation wavelength, sample temperature, and laser power. Although dephasing processes of optical transitions in solids are of considerable interest, they are poorly understood, largely due to the lack of experimental data on femtosecond and picosecond time scales. The APE technique using sub-picosecond laser sources has made it possible to measure in the time domain dephasing rates of inhomogeneously broadened transitions in amorphous systems.1,2
An analytic theory and experimental studies of the accumulated photon echo is presented. We define a temporal correlation function
G~ of the excitation field E ( t ) as
G~(τ,t)=(1/T1)∫0∞dt′E(t−t′)E(t−t′−τ)⋅exp(−t′/T1), where T 1 is the population relaxation time of the sample, and call the width of
G~ with respect to τ a temporal correlation time
τ~c(t). It is proved that the echo intensity is written by the temporal correlation functions when (1) T 1 and the duration of the excitation light τ p are much longer than
τ~c(t) in order to make the function
G~((τ,t) well-defined, (2) T 1 and τ p are much longer than the homogeneous dephasing time T 2 , and (3) one can find a time interval Δ t such that
G~(τ,t) does not change much between t and t + Δ t , where
Δt≫τ~c. Then we can show that the time resolution of the accumulated photon echo is determined by the averaged
τ~c(t) over an interval of the integration of the echo signal. This discussion is valid for any excitation source if the above conditions are satisfied, and applies to almost all cases of the practical accumulated photon echo experiment. A discussion is also made on the spurious spike on the echo decay curve near zero delay time that appeared in an experiment with a high time resolution in Nd 3+ -doped silicate glass. It is shown that the most probable cause for this spike is uncorrelated inhomogeneous broadenings of the resonant lines of neodymium ions.
Phase relaxation of optical excitations in condensed matter can be studied by coherent four—wave—mixing experiments in the time domain without requiring assumptions on the spectral properties of the material. For inhomogeneously broadened transitions, three laser pulses at times t = 0, t = t21 and t = T with wave vectors k1, k2 and k3, respectively, generate a stimulated photon echo pulse, emitted time—delayed at t = T+t21 in the momentum—matching direction according to k3+k2−k1. As a function of t21 the echo amplitude decays due to scattering events, described by the dephasing time constant T2 [1].