Coherent anti-Stokes Raman Spectra Research Articles

Analysis of picosecond coherent anti-Stokes Raman spectra for gas-phase diagnostics

We present a hybrid frequency- and time-domain solution, applicable to the case of picosecond coherent anti-Stokes Raman scattering (CARS), for gas-phase diagnostics. A solution has been derived based on both physical arguments and four-wave mixing equations for picosecond CARS, with pulse durations that are comparable to the dephasing time scale for gas-phase Raman coherence—a regime where commonly employed solutions for impulsive (femtosecond) or cw (nanosecond) pump/Stokes forcing are not strictly valid. We present the ps-CARS spectrum in the form of incoherent sums of CARS intensity spectra, calculated from the fundamental solution for impulsive pump/Stokes Raman preparation. The solution was examined for temperatures from 1000–3000 K, for four plausible experimental configurations, with laser pulse durations of 50–150 ps, and probe pulse delays from −20 to 240 ps. Approximations based on cw and impulsive pump/Stokes preparation to fit picosecond CARS spectra at atmospheric pressure were examined and the relative thermometric accuracy and computational cost of these approximations were quantified for the case of a zero nonresonant CARS contribution, and a nonresonant susceptibility equal to 10% of the Raman-resonant value at the N2 bandhead. The nanosecond CARS approximation can result in large fitting errors when the probe pulse time delay is less than the probe pulse duration. Errors as large as 10–20% are observed in the fit temperatures for a zero picosecond probe pulse delay, when the nonresonant background is neglected, largely due to an inability of the time-independent cw model to capture transient frequency spread dephasing effects at the Q-branch bandhead. The inclusion of a nonresonant background results in 40–60% thermometry errors with a nanosecond model at a zero-probe delay. Time-dependent impulsive calculations used for femtosecond CARS better approximate the structure of the N2 bandhead, reducing temperature fitting errors to 5–10% at a short probe pulse delay. The impulsive approximation results in errors up to 10% at intermediate probe pulse delays, where the coherence of the pump and probe pulses leads to multiple terms in the picosecond CARS solution. Both approximations improve as the probe pulse delay exceeds the probe duration. The nanosecond approximation results in a 2–3% error, while the impulsive model results in differences of less than 1% in some cases. Fits to experimental data obtained using short, ∼60ps pulses at a zero probe time delay and longer 100 ps pulses at a substantial 200 ps delay are presented with accuracies of 1–3% in the fit temperature.

Experimental investigations on rotation–vibration energy transfer in H2–N2 collisions

We investigated the rotational–vibrational impact energy transfer processes in a H2–N2 gas mixture system. The stimulated Raman pumping technique was used to excite H2 molecules to the (1, 7) high rotational states. The population of the H2(1, 7) level was verified by the coherent anti-Stokes Raman (CARS) spectra, the total pressure of the mixture was maintained at 500 Torr and nitrogen with different molar ratios was filled in the sample cell. The collisional deactivation rate coefficients of the excited state H2(1, 7) with H2 and N2 were obtained by fitting the experimental data with the Stern–Volmer equation. The multi-quantum near-resonant rotational relaxation process of H2(1, 7) colliding with N2 was confirmed by the time-resolved CARS profile measurements of H2(v = 1, J = 7, 5, 3) after the excitation of H2(1, 7). The results can provide data reference for atomic and molecular physics, atomic and molecular collisions, rotation and vibration excitation calculation, etc.

Vibrational spectroscopy of shock compressed condensed phase nitrous oxide: Frequency shifts in the ν1 mode

Over many years, we have published vibrational spectra of molecular materials at extreme pressure and temperature obtained using shock compression and coherent Raman spectroscopy methods. For diatomic molecules, we were able to extract vibrational temperatures from the intensities of spectrally resolved vibrational hot bands. Larger molecules in the condensed phase suffer band broadening effects that obscure the vibrational hot bands as the anharmonicities are typically smaller than the widths of the bands. This inability to resolve the hot bands inhibits the extraction of vibrational temperature and the measurement of the vibrational frequency of the fundamental. Here, we use a hot band model based on gas-phase anharmonic coupling coefficients to fit coherent anti-Stokes Raman spectra of the ν1 vibrational mode of shock compressed condensed phase N2O with shock pressures and temperatures estimated from literature equations of state and compare to fits from a model using a single Gaussian peak. We report the resulting vibrational frequency shifts with shock pressure.

Deep learning as phase retrieval tool for CARS spectra.

Finding efficient and reliable methods for the extraction of the phase in optical measurements is challenging and has been widely investigated. Although sophisticated optical settings, e.g. holography, measure directly the phase, the use of algorithmic methods has gained attention due to its efficiency, fast calculation and easy setup requirements. We investigated three phase retrieval methods: the maximum entropy technique (MEM), the Kramers-Kronig relation (KK), and for the first time deep learning using the Long Short-Term Memory network (LSTM). LSTM shows superior results for the phase retrieval problem of coherent anti-Stokes Raman spectra in comparison to MEM and KK.

Coherent Anti-Stokes-Stokes Raman Cross-Correlation Spectroscopy: Asymmetric Frequency Shifts in Hydrogen-Bonded Pyridine-Water Complexes.

Hydrogen bonding is a vital molecular interaction for bio-molecular systems, yet deep understanding of its ways of creating various complexes requires extensive empirical testing. A hybrid femtosecond/picosecond coherent Raman spectroscopic technique is applied to study pyridine-water complexes. Both the coherent Stokes and anti-Stokes Raman spectra are recorded simultaneously as the concentration of water in pyridine varied. A 3 ps and 10 cm-1 narrowband probe pulse enables us to observe well-resolved Raman spectra. The hydrogen bonding between pyridine and water forms the complexes that have altered vibrational frequencies. These red and blue shifts were observed to be uneven. This asymmetry was result of the generated background nonlinear optical processes of pyridine-water complexes. This asymmetry tends to disappear as probe pulse further delayed attaining background-free coherent Raman spectra. For better visualization, spectral analyses both traditional two-dimensional correlation spectroscopy and recent second-order correlation functions defined in frequency domain are employed. Recognized as a label-free and background-free technique, the coherent Raman spectroscopy, complemented with a known high-resolution spectroscopic correlation analysis, has potential in studying the hydrogen-bonded pyridine-water complexes. These complexes are of great biological importance both due to the ubiquitous nature of hydrogen bonds and due to the close resemblance to chemical bases in macro-biomolecules.

Dispersive Fourier transformation for megahertz detection of coherent stokes and anti-stokes Raman spectra

In many fields of study, from coherent Raman microscopy on living cells to time-resolved coherent Raman spectroscopy of gas-phase turbulence and combustion reaction dynamics, the need for the capability to time-resolve fast dynamical and nonrepetitive processes has led to the continued development of high-speed coherent Raman methods and new high-repetition rate laser sources, such as pulse-burst laser systems. However, much less emphasis has been placed on our ability to detect shot to shot coherent Raman spectra at equivalently high scan rates, across the kilohertz to megahertz regime. This is beyond the capability of modern scientific charge coupled device (CCD) cameras, for instance, as would be employed with a Czerny-Turner type spectrograph. As an alternative detection strategy with megahertz spectral detection rate, we demonstrate dispersive Fourier transformation detection of pulsed (∼90 ps) coherent Raman signals in the time-domain. Instead of reading the frequency domain signal out using a spectrometer and CCD, the signal is transformed into a time-domain waveform through dispersive Fourier transformation in a long single-mode fiber and read-out with a fast sampling photodiode and oscilloscope. Molecular O- and S-branch rotational sideband spectra from both N2 and H2 were acquired employing this scheme, and the waveform is fitted to show highly quantitative agreement with a molecular model. The total detection time for the rotational spectrum was 20 ns, indicating an upper limit to the detection frequency of ∼50 MHz, significantly faster than any other reported spectrally-resolved coherent anti-Stokes Raman detection strategy to date.

A unique approach to the vapour phase of the HIx feed of the sulfur iodine thermochemical cycle: A Raman spectroscopy study

The Sulfur Iodine cycle has great potential for large scale hydrogen production from water. The HIx processing stage (Section III) of the cycle exhibits the major challenges. Among them, experimental vapour liquid equilibrium data is scarce, mainly due to inherent hurdles to monitor the system under operating conditions of this section, i.e. temperature, acidity, and corrosion. Until now, UV–Visible and FTIR spectroscopies are the online monitoring techniques of choice, however due their selection rules, there is no experimental spectroscopic evidence of H2 during direct decomposition of HIx. Bearing this in mind, here we demonstrate the feasibility of exploiting two different Raman spectroscopic techniques as in situ monitoring tools, to gain substantial knowledge on the mechanisms of hydrogen production in Section III. Whereas resonance Raman spectra revealed the occurrence of HI·(H2O)3 in the vapour phase; coherent anti-Stokes Raman spectra of H2 allowed us to estimate kinetic data such as the activation energy for HI decomposition of a given hyper-azeotropic ternary mixture (i.e. xHI: 0.144; xI2:0.308; xH2O:0.548) is 149.15 kJ/mol.

Multiplexing single-beam coherent anti-stokes Raman spectroscopy with heterodyne detection

Multiplex detection of single beam coherent anti-Stokes Raman spectra is achieved by phase shaping of a narrow gate probe. The spectrally resolved signal is amplified via a local oscillator derived from the same single beam and is disentangled via double quadrature spectral interferometry. Spectral resolution and spectral range are defined by the width and position of the phase gate, which can be easily set by a femtosecond pulse shaper. Such phase-only multiplexed single beam coherent anti-Stokes Raman spectroscopy is demonstrated for simple molecules and is combined with Raman line reconstruction methods to obtain dispersion free Raman resonances.

Use of the Gerchberg–Saxton algorithm in optimal coherent anti-Stokes Raman spectroscopy

We are utilizing recent advances in ultrafast laser technology and recent discoveries in optimal shaping of laser pulses to significantly enhance the stand-off detection of explosives via control of molecular processes at the quantum level. Optimal dynamic detection of explosives is a method whereby the selectivity and sensitivity of any of a number of nonlinear spectroscopic methods are enhanced using optimal shaping of ultrafast laser pulses. We have recently investigated the Gerchberg-Saxton algorithm as a method to very quickly estimate the optimal spectral phase for a given analyte from its spontaneous Raman spectrum and the ultrafast laser pulse spectrum. Results for obtaining selective coherent anti-Stokes Raman spectra (CARS) for an analyte in a mixture, while suppressing the CARS signals from the other mixture components, are compared for the Gerchberg-Saxton method versus previously obtained results from closed-loop machine-learning optimization using evolutionary strategies.

Hyperspectral coherent anti-Stokes Raman scattering microscopy imaging through turbid medium

Coherent Raman microspectroscopy imaging is an emerging technique for noninvasive, chemically specific optical imaging, which can be potentially used to analyze the chemical composition and its distribution in biological tissues. In this report, a hierarchical cluster analysis was applied to hyperspectral coherent anti-Stokes Raman imaging of different chemical species through a turbid medium. It was demonstrated that by using readily available commercial software (Cytospec, Inc.) and cluster analysis, distinct chemical species can be imaged and identified through a rather thick layer of scattering medium. Once the clusters of different chemical composition were distinguished, a phase retrieval algorithm was used to convert coherent anti-Stokes Raman spectra to Raman spectra, which were used for chemical identification of hidden microscopic objects. In particular, applications to remote optical sensing of potential biological threats and to imaging through a layer of skin tissue were successfully demonstrated.

Coherent control of multiple vibrational excitations for optimal detection

While the means to selectively excite a single vibrational mode using ultrafast pulse shaping are well established, the subsequent problem of selectively exciting multiple vibrational modes simultaneously has been largely neglected. The coherent control of multiple vibrational excitations has applications in control of chemistry, chemical detection and molecular vibrational quantum information processing. Using simulations and experiments, we demonstrate that multiple vibrational modes can be selectively excited with the concurrent suppression of multiple interfering modes by orders of magnitude. While the mechanism of selectivity is analogous to that of single mode selectivity, the interferences required to select multiple modes require complicated non-intuitive pulse trains. Additionally, we show that selective detection can be achieved by the optimal pulse shape, even when the nature of the interfering species is varied, suggesting that optimized detection should be practical in real world applications. Experimental measurements of the multiplex coherent anti-Stokes Raman spectra (CARS) and CARS decay times of toluene, acetone, cis-stilbene and nitromethane liquids are reported, along with optimizations attempting to selectively excite nitromethane in a mixture of the four solvents. The experimental implementation exhibits a smaller degree of signal to background enhancement than predicted, which is primarily attributed to the single objective optimization methodology and not to fundamental limitations.

Herman–Wallis factor to improve thermometric accuracy of vibrational coherent anti-Stokes Raman spectra of H2

The Herman–Wallis factor is a molecular parameter that measures the influence of centrifugal force on the intensity of spectral lines. Understandably, the effect is significant for very light molecules that necessarily have large couplings between vibrational and rotational degrees of freedom. Although known, the conceptual basis of the Herman–Wallis factor are nevertheless not clearly established in the literature. Over the years, different approaches have been proposed to explain the corrections to spectral line-strengths and, recently, an experimental study has demonstrated that Q-branch Raman transitions of H2 are highly sensitive to the theoretical model employed to determine the Herman–Wallis factor. In this paper, this fact is used to analyze the consequences on thermometry based on coherent anti-Stokes Raman scattering (CARS) designed to probe H2 molecules in combustion studies. It is found that the different Herman–Wallis factors lead to relative thermometric disagreements from several tens up to hundreds of degrees. This analysis could explain why H2 CARS thermometry has been considered less reliable than thermometric predictions based on CARS of more common molecules such as N2, O2 and others. In particular, it is remarked that unreliable expressions of Herman–Wallis factors have been used so far to interpret Q-branch H2 CARS experiments.

Influence of Electronic Resonances on Mode Selective Excitation with Tailored Laser Pulses

Femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) gives access to ultrafast molecular dynamics. However, the gain of the temporal resolution entails a poor spectral resolution due to the inherent spectral width of the femtosecond excitation pulses. Modifications of the phase shape of one of the exciting pulses results in dramatic changes of the mode distribution reflected in coherent anti-Stokes Raman spectra. A feedback-controlled optimization of specific modes making use of phase and/or amplitude modulation of the pump laser pulse is applied to selectively influence the anti-Stokes signal spectrum. The optimization experiments are performed under electronically nonresonant and resonant conditions. The results are compared and the role of electronic resonances is analyzed. It can be clearly demonstrated that these resonances are of importance for a selective excitation by means of phase and amplitude modulation. The mode selective excitation under nonresonant conditions is determined mainly by the variation of the spectral phase of the laser pulse. Here, the modulation of the spectral amplitudes only has little influence on the mode ratios. In contrast to this, the phase as well as amplitude modulation contributes considerably to the control process under resonant conditions. A careful analysis of the experimental results reveals information about the mechanisms of the mode control, which partially involve molecular dynamics in the electronic states.

Mode-focusing in molecules by feedback-controlled shaping of femtosecond laser pulses

The feasibility of mode-selective excitation with broadband femtosecond laser pulses is demonstrated for toluene in liquid phase. A learning-loop optimal control scheme was applied to a stimulated Raman excitation process. Modifications of the phase shape of one of the exciting pulses resulted in dramatic changes of the mode distribution reflected in coherent anti-Stokes Raman spectra. An evolutionary algorithm guided the coherent excitation process to a selective enhancement or suppression of one or more vibrational modes over the complete coherence lifetime spanning several picoseconds. New ways of spectral filtering as well as exciting possibilities of mode-selective studying of chemical reaction dynamics are indicated.

Femtosecond phase-and-polarization control for background-free coherent anti-Stokes Raman spectroscopy.

Phase-and-polarization coherent control is applied to control the nonlinear response of a quantum system. We use it to obtain high-resolution background-free single-pulse coherent anti-Stokes Raman spectra. The ability to control both the spectral phase and the spectral polarization enables measurement of a specific off-diagonal susceptibility tensor element while exploiting the different spectral response of the resonant Raman signal and the nonresonant background to achieve maximal background suppression.

Single-pulse coherent anti-Stokes Raman spectroscopy in the fingerprint spectral region

Quantum coherent control techniques are applied to achieve high spectral resolution nonlinear vibrational spectroscopy using a single ultrashort laser source. By controlling the spectral phase of ∼10 fs pulses, we are able to obtain detailed coherent anti-Stokes Raman (CARS) spectra in the important fingerprint spectral region, which reflects the structural chemical information. A full theoretical analysis and an experimental demonstration of two alternative schemes leading to spectral resolution two orders of magnitude better than the pulse bandwidth are presented. The first involves selective excitation of vibrational levels within the pulse bandwidth by periodic modulation of the spectral phase of the pulse. In the second scheme an effective narrow probing of the vibrational level has been achieved by phase shifting of a narrow spectral band. Single-pulse CARS offers an attractive alternative to conventional multibeam nonlinear vibrational spectroscopy techniques.

High resolution coherent anti-Stokes Raman spectra of the Q-branches of the ?1 bands of14NH3 and15NH3 and their assignment

The Q-branches of the ν1 fundamental bands of 14NH3 and 15NH3 were recorded by continuous-wave coherent anti-Stokes Raman spectroscopy (CARS) at different pressures. Examples of the spectra at pressures from 1.4 to 5.0 kPa and the assignment of the observed lines are presented. For 14NH3 new experimental values for the Raman wavenumbers of K = 0 transitions were determined and for 15NH3 experimental wavenumbers of 71 IR and 56 Raman transitions are listed. Copyright © 2000 John Wiley & Sons, Ltd.

Assignment of coherent anti-stokes Raman spectra of the ν1 bands of ammonia: 14ND3 and 15ND3

High-resolution FTIR spectra of the ν1 bands of both 14ND3 and 15ND3 species were recorded with the Bruker spectrometer in Giessen. The spectra were assigned using the interactive program combining the Loomis-Wood technique with ground state combination difference checks. New sets of molecular constants of the ν1 vibrational levels of both isotopomers are presented. The ν1 rovibrational energies derived from the frequencies of the assigned transitions have made possible calculations of the Raman transition frequencies required for a simulation of the Coherent Anti-Stokes Raman Scattering (CARS) spectra. A satisfactory agreement of the simulated CARS spectra with the experimental ones was achieved.

Coherent anti-Stokes vibrational Raman spectra of artificial rhodopsin pigments containing ring structures blocking 11-cis isomerization

The structural changes in the retinal chromophore that underlie the initial picosecond processes in the room temperature rhodopsin (RhRT) photo-reaction (i.e., photoRT and bathoRT intermediates) are examined through the vibrational spectra of four artificial Rh pigments (new vibrational spectra from three artificial Rh pigments are presented here). Each of these Rh pigments contains a retinal in which isomerization around the C11C12 bond, thought to be the primary reaction coordinate in the RhRT photo-reaction, is blocked. Specifically, vibrational spectra from the ground electronic states of Rh7.10 (containing a 7-membered carbon ring spanning the C10–C11C12–C13 bonds in the retinal), Rh7.10/8D (Rh7.10 containing a deuterium at C8), Rh7.10/ND (Rh7.10 containing a deuterium at the Schiff-base nitrogen) and Rh8.10 (containing an 8-membered carbon ring spanning the C10–C11C12–C13 bonds in the retinal) are recorded by picosecond resonance coherent anti-Stokes Raman spectroscopy (PR/CARS). These PR/CARS data are analyzed with the aid of vibrational mode, assignments originating with native Rh used to identify the structural motions that can be associated with specific vibrational features. These PR/CARS assignments provide the spectroscopic information required to interpret the structural changes in the retinal chromophore, observed via picosecond time-resolved CARS measurements (reported elsewhere), following optical excitation of these same artificial Rh pigments. The relationships between structural changes in these artificial Rh pigments and those occurring in native Rh are also discussed.

Laser spectroscopy with a pulsed, narrowband infrared optical parametric oscillator system: a practical, modular approach

in a single scan. The potential of the OPO system for linear and nonlinear-optical spectroscopy is demonstrated by recording high-resolution photoacoustic absorption and coherent anti-Stokes Raman spectra of methane, as a gas and in a pulsed supersonic free jet. This narrowband tunable infrared source is shown to scan reliably with an optical bandwidth as small as 0.007 cm-1 (210 MHz) full width half maximum (fwhm), close to the fourier-transform limit.