We extend a recently formulated coherence spectroscopy of dissipative media [J. Chem. Phys. 122, 084502 (2005)] from the stationary excitation limit to the time domain. Our results are based on analytical and numerical solutions of the quantum Liouville equation within the Bloch framework. It is shown that the short pulse introduces a new, controllable time scale that allows better insight into the relation between the coherence signal and the phase properties of the material system. We point to the relation between the time-domain coherence spectroscopy and the method of interferometric two-photon photoemission spectroscopy, and propose a variant of the latter method, where the two time-delayed excitation pathways are distinguishable, rather than identical. In particular, we show that distinguishability of the two excitation pathways introduces the new possibility of disentangling decoherence from population relaxation.
We address the possibility of using coherent control tools to extract useful information about the interaction of a system with a dissipative environment. To that end we extend previous work, which developed a coherence spectroscopy based on two-pathway excitation phase control, from the isolated molecule limit to dense media. Specifically, we explore the properties of the channel phase, an observable of energy-domain two-pathway excitation experiments that was shown in the isolated molecule limit to carry information about the phase properties of the material system. Our analysis is based on the combination of steady state and time-dependent analytical perturbative approaches within the density matrix formalism, complemented by nonperturbative numerical simulations. We find that the channel phase carries significantly richer information in the presence of decoherence mechanisms than in their absence. In particular, rescattering events in the structured continuum introduce new features in the channel phase spectrum, whose structure conveys information about both the molecular continuum and the system bath interaction.
Dephasing-induced resonances, arising from interference between different excitation pathways, are well-known in frequency-domain spectroscopy.[1] It is generally thought that the time-domain analog of this phenomena is difficult to achieve due to the explicit time ordering of the interaction fields.[2,3] In this contribution we report on the observation of time-domain interference in phase-locked stimulated photon echo. We also show how complete control over the interference effect can be exercised.
We have developed a general technique for obtaining analytical expressions for coherent transient signals arising from atoms interacting with two or more laser pulses having Gaussian spatial profiles. After deriving the Maxwell-Bloch equations for short laser pulses incident on an ensemble of three-level atoms, we specialize to photon echo spectroscopy. As an example, the stimulated photon echo signal is calculated as a function of the time delay between pulses. Our exact results are compared with both the lowest-order perturbative limit and a calculation in which transit time is treated phenomenologically. We conclude by commenting on the extension of our technique to atoms undergoing velocity-changing collisions. \textcopyright{} 1996 The American Physical Society.
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.
In this series of papers we report on the generation and application of multiple pulse phase coherent sequences in optical spectroscopy.In this paper the effects of intense pulse trains on systems with only two resonant energy levels are analyzed, with particular attention to the effects of extreme inhomogeneous broadening and population depletion to nonresonant levels.It is shown that these effects, which are present in virtually all optical systems, make the simple gyroscopic model of optical coherent transients invalid.Exact calculations show, e.g., that a two-pulse photon echo is not maximized by a 1:2 length ratio for the pulses; that the maximum excited state population is not created by a 180" pulse; and that three equal pulses are almost as effective as a 1:2:1 ratio for producing three pulse echoes.The role of pulse phase is extensively analyzed.Pulse sequences are proposed and experimentally demonstrated which permit optical phase sensitive detection and measurement of ground state relaxation parameters.The experimental results are based on an extension of the acousto-optic modulation and fluoresence detection techniques of Zewail and Orlowski [Zewail et al., Chem.Phys.Lett.48, 256 (1977); Orlowski et al., ibid.54, 197 (1978)).The relative merits offluorescence and transverse polarization detection are discussed, and fluorescence detection is shown to be more generally useful for these new sequences.Finally, composite pulse trains are shown to be capable of substantially increasing the signal available from highly inhomogenously broadened transitions.In paper II we extend the treatment to multilevel systems with some emphasis on solid state applications.
In recent years, frequency-comb-based multidimensional coherent spectroscopy has emerged as a very powerful optical method for studying samples with long dephasing times. It enables the measurement of comb resolution multidimensional coherent spectra in seconds as opposed to hours or even days required by traditional mechanical stage-based spectrometers. However, for some samples (e.g., cold atoms and molecules) the dephasing times could be longer than the repetition periods of the excitation lasers which means that the generated signal will not fully decay between the pulses. Depending on the relative phase or time between the pulses, the signals generated by the subsequent laser pulses can constructively or destructively interfere with each other. In this paper we study this behavior by solving the optical Bloch equations and provide a theoretical description of frequency-comb-based multidimensional coherent spectroscopy.