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The Journal of Physical Chemistry A

Pulse Propagation Effects in Optical 2D Fourier-Transform Spectroscopy: Theory

Austin P. Spencer, Hebin Li, Steven T. Cundiff, David M. Jonas

Published Apr 16, 2015• 42 citations
Publisher

Abstract

A solution to Maxwell's equations in the three-dimensional frequency domain is used to calculate rephasing two-dimensional Fourier transform (2DFT) spectra of the D2 line of atomic rubidium vapor in argon buffer gas. Experimental distortions from the spatial propagation of pulses through the sample are simulated in 2DFT spectra calculated for the homogeneous Bloch line shape model. Spectral features that appear at optical densities of up to 3 are investigated. As optical density increases, absorptive and dispersive distortions start with peak shape broadening, progress to peak splitting, and ultimately result in a previously unexplored coherent transient twisting of the split peaks. In contrast to the low optical density limit, where the 2D peak shape for the Bloch model depends only on the total dephasing time, these distortions of the 2D peak shape at finite optical density vary with the waiting time and the excited state lifetime through coherent transient effects. Experiment-specific conditions are explored, demonstrating the effects of varying beam overlap within the sample and of pseudo-time domain filtering. For beam overlap starting at the sample entrance, decreasing the length of beam overlap reduces the line width along the ωτ axis but also reduces signal intensity. A pseudo-time domain filter, where signal prior to the center of the last excitation pulse is excluded from the FID-referenced 2D signal, reduces propagation distortions along the ωt axis. It is demonstrated that 2DFT rephasing spectra cannot take advantage of an excitation-detection transformation that can eliminate propagation distortions in 2DFT relaxation spectra. Finally, the high optical density experimental 2DFT spectrum of rubidium vapor in argon buffer gas [J. Phys. Chem. A 2013, 117, 6279-6287] is quantitatively compared, in line width, in depth of peak splitting, and in coherent transient peak twisting, to a simulation with optical density higher than that reported.

DOI
10.1021/acs.jpca.5b00001

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A solution to Maxwell's equations in the three-dimensional frequency domain is used to calculate rephasing two-dimensional Fourier transform (2DFT) spectra of the D2 line of atomic rubidium vapor in argon buffer gas. Experimental distortions from the spatial propagation of pulses through the sample are simulated in 2DFT spectra calculated for the homogeneous Bloch line shape model. Spectral features that appear at optical densities of up to 3 are investigated. As optical density increases, absorptive and dispersive distortions start with peak shape broadening, progress to peak splitting, and ultimately result in a previously unexplored coherent transient twisting of the split peaks. In contrast to the low optical density limit, where the 2D peak shape for the Bloch model depends only on the total dephasing time, these distortions of the 2D peak shape at finite optical density vary with the waiting time and the excited state lifetime through coherent transient effects. Experiment-specific conditions are explored, demonstrating the effects of varying beam overlap within the sample and of pseudo-time domain filtering. For beam overlap starting at the sample entrance, decreasing the length of beam overlap reduces the line width along the ωτ axis but also reduces signal intensity. A pseudo-time domain filter, where signal prior to the center of the last excitation pulse is excluded from the FID-referenced 2D signal, reduces propagation distortions along the ωt axis. It is demonstrated that 2DFT rephasing spectra cannot take advantage of an excitation-detection transformation that can eliminate propagation distortions in 2DFT relaxation spectra. Finally, the high optical density experimental 2DFT spectrum of rubidium vapor in argon buffer gas [J. Phys. Chem. A 2013, 117, 6279-6287] is quantitatively compared, in line width, in depth of peak splitting, and in coherent transient peak twisting, to a simulation with optical density higher than that reported.
Two-dimensional Fourier-transform (2DFT) spectra of the D2 line of rubidium vapor in argon buffer gas are simulated using a three-dimensional frequency domain solution of Maxwell's equations that treats linear propagation distortions exactly. Simulations for the homogeneous optical Bloch model at optical densities of up to 3 are compared to measured rephasing 2DFT spectra. Experimentally observed propagation distortions are qualitatively reproduced in calculated 2DFT spectra, including peak broadening, peak splitting, and peak twisting. Varying beam overlap through the sample is crudely modeled in simulations, demonstrating that reduced beam overlap causes narrowing of the peak shape in the excitation dimension and an overall reduction in signal size. Propagation distortions, including peak splitting depth and peak twist, are found to vary with waiting time and with the excited state lifetime at a fixed total dephasing time, suggesting a coherent mechanism.\nA new method for reducing repetitive excitation of the sample by scanning beams with respect to a stationary sample cell using a fast steering mirror is described. This apparatus extends the average time between excitations at any point in the sample to >0.3 s and accommodates a wide variety of sample cell formats, including cryostats, air-tight cuvettes, and flow cells.\nColloidal indium arsenide (InAs) quantum dots (QDs) are interrogated by degenerate pump{ probe transient absorption spectroscopy at a photon energy of approximately 1.5 times the band gap using spatially-averaged excitation probabilities lower than in previously reported studies. Signatures of Auger recombination appear with a timescale of 26 +/- 5 ps. Carrier cooling and recombination pathways are explored, revealing new dynamics not observed in studies that probe the band edge.
Optical two-dimensional Fourier-transform (2DFT) spectroscopy is used to study the coherent optical response of potassium vapor in a thin transmission cell. Rephasing and nonrephasing spectra of the D1{D}_{1}D1​ and D2{D}_{2}D2​ transitions are obtained and compared to numerical simulations. Non-perturbative calculations using the optical Bloch equations give very good agreement with the experimental peak strengths and line shapes. Nonradiative Raman-like coherences are isolated using a different 2DFT projection. Comparison between the optical and Raman linewidths shows that dephasing is due to partially correlated energy fluctuations. Density-dependent measurements show distortion of 2DFT spectra due to pulse propagation effects.
Two-dimensional (2D) spectroscopy is a powerful pump-pump-probe technique for revealing couplings between quantum states and disentangling the different contributions to the optical response of a system. We present an efficient method for 2D spectroscopy simulations in the Markovian limit for the environment, capable of handling arbitrary pulse shapes and reproducing time-ordering and overlapping pulse effects, while maintaining a computational cost that scales linearly with the number of sampling points. We leverage this framework to investigate how 2D spectra are affected by spectral phase distortions and highly non-Gaussian pulse shapes, such as those produced experimentally by hollow-core fibers or non-collinear optical amplifiers. We show that realistic pulses can induce the appearance of additional spectral features, lineshape distortions and oscillating contributions in the system's dynamics. Notably, even weak temporal pulse tails arising from uncorrected high-order spectral phase terms cause visible changes in the 2D spectra. We also find that homodyne detection schemes employed in experiments can mitigate the presence of such pulse effects. These results emphasize the importance of including realistic pulses in 2D spectroscopy simulations to identify pulse-induced effects and minimize ambiguities in the interpretation of experimental data.
Two-dimensional (2D) line shapes derived from four types of coherent third-order nonlinear spectroscopies as a function of two independent time or frequency variables are compared. The signals scattered into two wave-vector-matching directions in the limits of high-time or high-frequency resolution are calculated for an inhomogeneously broadened ensemble of two-level systems with phenomenological dephasing and population relaxation times. While one-dimensional (1D) line shape analysis for this model is ambiguous, the contours of these 2D line shapes are shown to be characteristic of the relative time scales of the three relevant line-broadening parameters. These broadening mechanisms are also apparent by comparing 2D spectral profiles along the diagonal and antidiagonal frequency axes. For time domain experiments, in analogy with NMR correlation spectroscopy, the radiated signal is observed as a function of the two coherence periods and is 2D Fourier transformed to obtain a line shape. For experiments based on the photon echo, the ellipticity of the absolute value 2D line shape is related to the ratio of the inhomogeneous width to the dephasing rate, whereas experiments based on the transient grating method are shown to be functionally 1D. For frequency domain experiments, the contours of the 2D line shape can yield information on static and both dynamic broadening mechanisms. While the addition of spectral diffusion to such calculations will modify these results for frequency domain experiments, characterizing these dynamics in the time domain naturally leads to a 3D experiment analogous to the spin diffusion experiment in NMR.
A theoretical analysis of the optical coherent transients that arise when a sample of two-level atoms is irradiated by a sequence of three broad-bandwidth pulses is presented. The first two pulses have a relative delay time of order of the correlation time of the pulse fluctuations and are sent into an atomic vapor from different directions. These pulses, whose temporal width is much greater than the delay time, can be correlated with one another and can be strong enough to saturate the two-level atomic transition. The third pulse is weak, noncorrelated with the first two, and is delayed in time so that it does not overlap them. We present a detailed examination of the transient signal that is produced when the third pulse is scattered by the spatial gratings in the population difference of atoms created by the first two pulses. Taking into account the effects of inhomogeneous and homogeneous broadening, we calculate the intensity of the transient signal, emitted in different directions, as a function of delay time. The signal is found to depend dramatically on the intensities of the excitation pulses. It is shown that, for strong excitation pulses, there is a direct dependence of the signal on the cross-correlation time of pulses ${\mathrm{\ensuremath{\tau}}}_{\mathit{c}}^{12}$ that does not exist when the pulses are weak. In particular, the strongest signals exhibit a peak of width of order ${\mathrm{\ensuremath{\tau}}}_{\mathit{c}}^{12}$. This peak can have a very narrow dip near its maximum whose width is much smaller than ${\mathrm{\ensuremath{\tau}}}_{\mathit{c}}^{12}$, if the pulses are fully correlated. We develop a representation of the time evolution of the Bloch vector of a two-level atom, driven by time-delayed pulses, that enables us to explain our results. In this representation, the two time-delayed pulses are replaced by two fully overlapping pulses having some effective amplitudes and atomic field detunings.
With the development of laser technology in the field of optics, ultra-fast optics has become an important research field. Compared with the traditional technology, ultrafast optics can be realized not only under shorter pulse function, but also on a smaller scale, which can more quickly reflect the dynamic process. We present an analytical calculation of the full three-dimensional (3D) coherent spectrum with a finite duration two-dimensional (2D) Gaussian pulse envelope. Our starting point is the solution of the optical Bloch equations for three-level potassium atomic gas in the 3D time domain by using the projection-slice theorem, error function and Fourier-shift theorem of 3D Fourier transform. These principles are used to calculate and simplify the third-order polarization equation generated by the device, and the analytical calculation of three-dimensional Fourier transform frequency spectrum at T = 0 is obtained. We simulate the analytic solution by using mathematics software. By comparing the simulations with the experimental results, with the homogeneous line-width fixed, we can obtain the relationship among the in-homogeneous broadening, the correlation diagonal coefficients and the three-dimensional spectrum characteristics, which can be identified quantitatively by fitting the slices of three-dimensional Fourier transform spectrum peaks in an appropriate direction. The results show that the three-dimensional Fourier transform spectrum will extend along the diagonal direction with the increasing of the in-homogeneous broadening, and the spectrogram progressively becomes a circle with the increasing of the diagonal correlation coefficient, and the amplitude also gradually turns smaller. According to the analytical solution, we give a complete two-dimensional spectrum of the T = 0 interface. The results can be fit to the experimental 3D coherent spectrum for arbitrary inhomogeneity.