A new method of picosecond and femtosecond transient spectroscopy yielding information about ultrafast relaxation processes without requiring ultrashort light pulses is presented. It is based on the present theoretical analysis of the resonant degenerate four-wave-mixing process excited by two temporally incoherent light beams with wave vectors ${\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{1}$ and ${\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{2}$ which are originated from a single beam at frequency $\ensuremath{\omega}$ but have mutual time delay $\ensuremath{\tau}$. Under the assumption that the incoherent light field has Gaussian random complex amplitude and that the resonant material consists of the usual two-level atoms, the statistically averaged intensity of the output light field with ${\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{3}=2{\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{2}\ensuremath{-}{\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}}_{1}$ at $\ensuremath{\omega}$ is calculated as a function of $\ensuremath{\tau}$. Even with the light having a much longer duration than both
T1 (the longitudinal relaxation time) and
T2 (the transverse relaxation time), the correlation trace, i.e., output intensity versus $\ensuremath{\tau}$, represents a decay profile determined mainly by
T2 for both homogeneously and inhomogeneously broadened transitions, as long as the light correlation time ${\ensuremath{\tau}}_{c}$ is much shorter than the relaxation times. The correlation trace does not always represent a single-exponential decay but is sometimes slightly deformed by the
T1 effect. However, it does not cause a significant error in the determination of
T2. Moreover, as $\frac{{T}_{2}}{{T}_{1}}\ensuremath{\rightarrow}0$, the trace becomes a single-exponential decay curve determined only by
T2. The feature of the results obtained by the present method is similar to that obtained by the conventional coherent transient spectroscopy with short pulses, such as the photon echo. The time resolution in the present method, however, is limited only by ${\ensuremath{\tau}}_{c}$ much shorter than the light duration. By regarding the incoherent light as a series of random ultrashort pulses, the present four-wave-mixing process is also interpreted as the ensemble of numerous transient four-wave-mixing processes caused by various combinations of these pulses.
The emergence of experiments capable of probing quantum dynamics at the single-molecule level requires the development of new theoretical tools capable of simulating and analyzing these dynamics beyond an ensemble-averaged description. In this article, we present an efficient method for sampling and simulating the dynamics of the individual quantum systems that make up an ensemble and apply it to study the nonequilibrium dynamics of the ubiquitous spin-boson model. We generate an ensemble of single-system trajectories, and we analyze this trajectory ensemble using tools from classical statistical mechanics. Our results demonstrate that the dynamics of quantum coherence is highly heterogeneous at the single-system level due to variations in the initial bath configuration, which significantly affects the transient exchange of coherence between the system and its bath. We observe that single systems tend to retain coherence over time scales longer than that of the ensemble. We also compute a novel thermodynamic entanglement entropy that quantifies a thermodynamic driving force favoring system-bath entanglement.
We review our recent advances in four-wave mixing spectroscopy of single semiconductor quantum dots using heterodyne spectral interferometry, a novel implementation of transient nonlinear spectroscopy allowing the study of the transient nonlinear polarization emitted from individual electronic transitions in both amplitude and phase. We present experiments on individual excitonic transitions localized in monolayer islands of GaAs/AlAs quantum wells and in self-assembled CdTe/ZnTe quantum dots. We investigate the formation of the photon echo from individual transitions, both with increasing number of transitions in the ensemble, and in the presence of temporal jitter of the energy of a single transition. The detection of amplitude and phase of the signal allows the implementation of a two-dimensional femtosecond spectroscopy, in which mutual coherent coupling of single quantum dot states can observed and quantified.