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We present spatially enhanced electric-field-induced second-harmonic (SEEFISH) generation with a chirped femtosecond beam for measurements of electric field in mesoscale confined geometries subject to destructive spurious second-harmonic generation (SHG). Spurious SHG is shown to interfere with the measured E-FISH signal coherently, and thus simple background subtraction is not sufficient for single-beam E-FISH approaches, especially in a confined system with a large surface-to-volume ratio. The results show that a chirped femtosecond beam is effective in preventing higher-order mixing and white light generation in windows near the beam focal point which further contaminates the SEEFISH signal. The successful measurements of electric field of a nanosecond dielectric barrier discharge in a test cell demonstrated that spurious SHG detected with a congruent traditional E-FISH approach can be eliminated using the SEEFISH approach.

We present time-domain measurements and modelling of the CH4 ν 1 vibrational Q-branch, as well as simultaneous temperature acquisition from the CH4 and N2 vibrational Q-branches using broadband hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Accurate measurements with fs/ps CARS require knowledge of the time-domain response of the probed molecule at different temperatures and pressures. In this work, a fs/ps CARS model was developed for the CH4 ν 1 Q-branch and validated using time-resolved probe delay scans at pressures between 70 and 600 Torr and temperatures between 295 and 1000 K. A simplified modified exponential energy gap model was used to determine the linewidths of the Raman transitions within the Q-branch. Total Q-branch linewidths for the entire explored parameter space were also determined from the probe delay scans. This enabled quantitative measurements of CH4 with fs/ps CARS as well as the temperature through the hot bands of the CH4 ν 1 Q-branch. With a broadband fs laser pulse in a two-beam phase matching scheme, the N2 Q-branch and CH4 ν 1 Q-branch were simultaneously measured in a heated cell, and the temperatures from each molecule's spectra was evaluated. The fitted temperatures corresponded well with differences ranging from 4 to 17%. It was also shown that exchanging 90% of CH4 for N2 or Ar at 295 K and 500 Torr did not significantly impact the normalized time-domain signal prior to a 100 picosecond probe delay. Spatially resolved one-dimensional (1-D) thermometry using the CH4 Q-branch was also demonstrated with an imaged spatial resolution of 40 µm. With the developed model, 1-D quantitative measurements of CH4 concentration and temperature can be measured with time resolution of tens of picoseconds.

The first detection of surface-bound free rotors with exceptionally long rotational and vibrational coherence lifetimes was detected for both CO and CH4 adsorption to Au at near-ambient pressures. Hybrid femtosecond/picosecond sum-frequency generation vibrational spectroscopy was used to detect rovibrational coherence recurrences with coherence lifetimes lasting several 10’s of picoseconds. The observations challenge our understanding of weak adsorption of molecules to metal surfaces.

We report the development of a simple and sensitive two-beam hybrid femtosecond/picosecond pure rotational coherent anti-Stokes Raman scattering (fs/ps CARS) method to simultaneously measure the rotational and vibrational temperatures of diatomic molecules. Rotation–vibration non-equilibrium plays a key role in the chemistry and thermalization in low-temperature plasmas as well as thermal loading of hypersonic vehicles. This approach uses time-domain interferences between ground state and vibrationally excited N2 molecules to intentionally induce coherence beating that leads to apparent non-Boltzmann distributions in the pure rotational spectra. These distortions enable simultaneous inference of both the rotational and vibrational temperatures. Coherence beating effects were observed in single-shot fs/ps CARS measurements of a 75 Torr N2 DC glow discharge and were successfully modeled for rotational and vibrational temperature extraction. We show that this method can be more sensitive than a pure rotational fs/ps CARS approach using a spectrally narrow probe pulse. Lastly, we experimentally measured the beat frequencies via Fourier transform of the time-domain response and obtained excellent agreement with the model.

We present one-dimensional (1-D) imaging of rotation-vibration non-equilibrium measured by two-beam pure rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman scattering (fs/ps CARS). Simultaneous measurements of the spatial distribution of molecular rotation-vibration non-equilibrium are critical for understanding molecular energy transfer in low temperature plasmas and hypersonic flows. However, non-equilibrium CARS thermometry until now was limited to point measurements. The red shift of rotational energy levels by vibrational excitation was used to determine the rotational and vibrational temperatures from 1-D images of the pure rotational spectrum. Vibrational temperatures up to 5500 K were detected in a C H 4 / N 2 nanosecond-pulsed pin-to-pin plasma within 2 mm near the cathode. This approach enables study of non-equilibrium systems with 40 µm spatial resolution.

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 N 2 and H 2 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.

Ultrabroadband coherent anti-Stokes Raman spectroscopy (CARS) has been developed for one-dimensional imaging of temperature and major species distributions simultaneously in the near-wall region of a methane/air flame supported on a side-wall-quenching (SWQ) burner. Automatic temporal and spatial overlap of the ∼7 fs pump and Stokes pulses is achieved utilizing a two-beam CARS phase-matching scheme, and the crossed ∼75 ps probe beam provides excellent spatial sectioning of the probed location. Concurrent detection of N2, O2, H2, CO, CO2, and CH4 is demonstrated while high-fidelity flame thermometry is assessed from the N2 pure rotational S-branch in a one-dimensional-CARS imaging configuration. A methane/air premixed flame at lean, stoichiometric, and rich conditions (Φ = 0.83, 1.0, and 1.2) and Reynolds number = 5000 is probed as it quenches against a cooled steel side-wall parallel to the flow providing a persistent flame–wall interaction. An imaging resolution of better than 40 µm is achieved across the field-of-view, thus allowing thermochemical states (temperature and major species) of the thermal boundary layer to be resolved to within ∼30 µm of the interface.

Time-resolved pure-rotational hybrid femtosecond/picosecond coherent anti-Stokes Raman spectroscopy (fs/ps RCARS) of oxygen (O2) is performed at pressures from ∼0.04 to 0.4 atm. As the RCARS spectra evolve with probe delay, they exhibit coherence beating between unresolved S-branch triplet transitions (ΔN = 2, ΔJ = 2). The time-domain fitting of the RCARS signal intensity enables the determination of these transition frequency separations, which are as low as 480 MHz (0.016 cm-1). Additionally, we study the underlying pressure-dependent dynamics and the signatures of the time-domain triplet signals compared to the simple decays associated with the O2 self-broadened linewidths. Pressure- and N-dependent O2 linewidths are compared to literature coefficients obtained from experiments and models that have not incorporated the triplet splitting. Our findings are incorporated into a time-domain model for rotational CARS thermometry of O2 and have significant impact for spectral evaluations at probe delays greater than 100 ps for temperature or species concentration determination. The time- and frequency-resolved experiments presented in this work provide insight into the spectroscopic complexities introduced by the electronic ground state of O2 for accurate evaluation of time-resolved coherent Raman spectra.

Coherent anti-Stokes Raman scattering (CARS) is a valuable spectroscopic tool for the measurement of temperature and species concentration. In recent years, multi-dimensional CARS has seen focused development and is especially important in reacting flows. An important aspect of multi-dimensional CARS is the phase-matching scheme used. Historically, collinear and BOXCARS phase-matching schemes have been used to achieve phase matching over a broad spectral range. For 1-D and 2-D CARS imaging, two-beam or counter-propagating beam arrangements are necessary. The two-beam arrangement offers many advantages, but introduces a phase mismatch which limits the spectral response of the measurement. This work explores the tradeoffs in spatial resolution, spectral bandwidth, and CARS intensity in 2-D CARS arrangements. Calculations are made for two-beam and counter-propagating beam CARS.

We demonstrate the use of hybrid rotational femtosecond/picosecond (fs/ps) coherent anti-Stokes Raman spectroscopy (HR-CARS) as a technique for temperature measurements in nitrogen gas at high pressures and temperatures. A broadband pulse shaper-adjusted 42 fs pulse interacts with a narrow-bandwidth, frequency-upconverted 5.5 ps pulse in a cell containing N 2 at pressures of 1–70 atm and temperatures of 300–1000 K. A computational code is used to model spectra and fit experimental results to obtain best-fit temperatures. We demonstrate good qualitative fits as well as good accuracy and precision between thermocouple measured and best-fit temperatures over the explored pressure and temperature regimes. The overall average percentage temperature difference between thermocouple measurements and best-fit temperatures is − 0 . 3 % with a standard deviation of 7.1%, showing the suitability of HR-CARS for characterizing high-pressure and -temperature environments.

A single-shot coherent Raman imaging technique has been developed for spatially correlated one-dimensional high-fidelity gas-phase thermometry and multiplex chemical detection in flames. The technique utilizes two-beam phase matching, operating a single ultrashort pump/Stokes excitation pulse (7 fs) and a narrowband picosecond probe pulse (70 ps), interrogating a Raman active window of ∼4200 cm(-1) with ∼0.3 cm(-1) spectral resolution. The measurement geometry is formed intersecting the two beams shaped as laser-sheets and the one-coordinate spatial information is retrieved with a linespread function of

Hybrid femtosecond/picosecond rotational coherent anti-Stokes Raman spectroscopy (CARS) is developed utilizing a two-beam phase-matching approach for one-dimensional (1D) measurements demonstrated in an impinging jet burner to probe time-resolved head on quenching (HOQ) of a methane/air premixed flame at Φ = 1.0 and Reynolds number = 5000. Single-laser-shot 1D temperature profiles are obtained over a distance of at least 4 mm by fitting the pure-rotational N 2 CARS spectra to a spectral library calculated from a time-domain CARS code. An imaging resolution of ∼61 μm is obtained in the 1D-CARS measurements. The acquisition of single-shot 1D CARS measurements, as opposed to traditional point-wise CARS techniques, enables new spatially correlated conditional statistics to be determined, such as the position, magnitude, and fluctuations of the instantaneous temperature gradient. The temperature gradient increases as the flame approaches the metal surface, and decreases during quenching. The standard deviation of the temperature gradient follows the same trend as the temperature gradient, increasing as the flame front approaches the surface, and decreasing after quenching.

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N

Spatial mapping of temperature and molecular species concentrations is vitally important in studies of gaseous chemically reacting flows. Temperature marks the evolution of heat release and energy transfer, while species concentration gradients provide critical information on mixing and chemical reaction. Coherent anti-Stokes Raman spectroscopy (CARS) was pioneered in measurements of such processes almost 40 years ago and is authoritative in terms of the accuracy and precision it may provide. While a reacting flow is fully characterized in three-dimensional space, a limitation of CARS has been its applicability as a point-wise measurement technique, motivating advancement toward CARS imaging, and attempts have been made considering one-dimensional probing. Here, we report development of two-dimensional CARS, with the first diagnostics of a planar field in a combusting flow within a single laser pulse, resulting in measured isotherms ranging from 450 K up to typical hydrocarbon flame temperatures of about 2000 K with chemical mapping of O2 and N2.

We demonstrate hybrid femtosecond/picosecond (fs/ps) pure-rotational coherent anti-Stokes Raman spectroscopy (RCARS) at high temperatures and pressures. Pulse-shaper-produced 40 fs pulses and bandwidth-narrowed, frequency-upconverted 5 ps pulses interact in a high-pressure cell containing N2 at 1–70 atm and 300–1000 K. Accurate experimental temperatures evaluated from fits to model rotational spectra confirm that the sensitivity and precision advantages of hybrid fs/ps RCARS can be exploited in characterizing combustion environments, even in the pressure regime where significant collisional energy transfer and line broadening cannot be neglected.

We extend an approach based upon sum-frequency generation of oppositely chirped pulses to narrow the bandwidths of broadband femtosecond pulses. We efficiently generate near-transform-limited pulses with durations of several picoseconds, while reducing the pulse bandwidth by a factor of 120, which is more than twice the reduction reported in previous literature. Such extreme bandwidth narrowing of a broadband pulse enhances the effects of dispersion nonlinearities. Precise chirp control enables us to characterize the efficacy of frequency mixing broadband pulses with nonlinear temporal chirps. We demonstrate the use of these narrowband pulses as probes in coherent anti-Stokes Raman spectroscopy.

Total N-2 S-branch broadening coefficients have been measured in situ as a function of radial position in a highly sooting ethylene diffusion flame by the use of time-resolved dual-broadband picosecond pure rotational CARS (RCARS). Time-domain measurements of the J-dependent N-2 rotational coherence decays in the flame were used to determine the broadening coefficients, and these coefficients were then used in the spectral fitting routine for the determination of temperature and [O-2]/[N-2] ratio in the flame. Corrections of up to 125 K are found when compared to spectral fitting using an ECS self-broadened N-2 linewidth model. The presented technique effectively takes into account contributions to the N-2 linewidths from all collision partners without any a priori knowledge of relative species concentrations. Published by Elsevier Inc. on behalf of The Combustion Institute. (Less)

Time-resolved dual-broadband picosecond pure rotational CARS has been applied to measure self-broadened S-branch N2–N2 Raman linewidths in the temperature range 294–1466 K. The coherence decays were detected directly in the time domain by following the J-dependent CARS signal decay as a function of probe delay. The rotational Raman N2–N2 linewidths were derived from these time-dependent decays and evaluated for thermometric accuracy. Comparisons were made to the energy-corrected sudden (ECS) and modified exponential gap (MEG) dynamical scaling laws, and the results were used to quantify the sensitivity of nanosecond rotational CARS thermometry to the linewidth model employed. The uncertainty based on the linewidth model used in pure N2 was found to be 2 %. The merits and limitations of this rapid method for the determination of accurate Raman linewidths are discussed.

The development of time-resolved dual-broadband pure-rotational coherent anti-Stokes Raman spectroscopy using picosecond laser pulses is investigated for use in the study of highly sooting flames. Axi-symmetric ethylene and propane diffusion flames were studied. Suppression of nonresonant and Raman resonant interference signals is demonstrated by delaying the probe pulse beyond the temporal envelope of the pump pulses, and these spectra are compared with those obtained using conventional polarization-based interference suppression techniques. Flame profiles for both temperature and the O 2 to N 2 ratio are obtained. Evaluated temperatures are corrected for delay-induced spectral heating and compared to published thermocouple measurements.

Sum-frequency generation vibrational spectroscopy (SFG-VS) and kinetic measurements using gas chromatography have been used to study the surface reaction intermediates during the hydrogenation of three alpha,beta-unsaturated aldehydes, acrolein, crotonaldehyde, and prenal, over Pt(111) at Torr pressures (1 Torr of aldehyde, 100 Torr of hydrogen) in the temperature range of 295-415 K. SFG-VS data showed that acrolein has mixed adsorption species of eta(2)-di-sigma(CC)-trans, eta(2)-di-sigma(CC)-cis as well as highly coordinated eta(3) or eta(4) species. Crotonaldehyde adsorbed to Pt(111) as eta(2) surface intermediates. SFG-VS during prenal hydrogenation also suggested the presence of the eta(2) adsorption species and became more highly coordinated as the temperature was raised to 415 K, in agreement with its enhanced C=O hydrogenation. The effect of catalyst surface structure was clarified by carrying out the hydrogenation of crotonaldehyde over both Pt(111) and Pt(100) single crystals while acquiring the SFG-VS spectra in situ. Both the kinetics and SFG-VS showed little structure sensitivity. Pt(100) generated more decarbonylation "cracking" product while Pt(111) had a higher selectivity for the formation of the desired unsaturated alcohol, crotyl alcohol.

The understanding of selectivity in heterogeneous catalysis is of paramount importance to our society today. In this review we outline the current state of the art in research on selectivity in heterogeneous catalysis. Current in-situ surface science techniques have revealed several important features of catalytic selectivity. Sum frequency generation vibrational spectroscopy has shown us the importance of understanding the reaction intermediates and mechanism of a heterogeneous reaction, and can readily yield information as to the effect of temperature, pressure, catalyst geometry, surface promoters, and catalyst composition on the reaction mechanism. DFT calculations are quickly approaching the ability to assist in the interpretation of observed surface spectra, thereby making surface spectroscopy an even more powerful tool. HP-STM has revealed three vitally important parameters in heterogeneous selectivity: adsorbate mobility, catalyst mobility and selective site-blocking. The development of size controlled nanoparticles from 0.8 to 10 nm, of controlled shape, and of controlled bimetallic composition has revealed several important variables for catalytic selectivity. Lastly, DFT calculations may be paving the way to guiding the composition choice for multi-metallic heterogeneous catalysis for the intelligent design of catalysts incorporating the many factors of selectivity we have learned.

Pyrrole Hydrogenation over Rh(111) and Pt(111) Single-Crystal Surfaces and Hydrogenation Promotion Mediated by 1-Methylpyrrole: A Kinetic and Sum- Frequency Generation Vibrational Spectroscopy Study Christopher J. Kliewer, Marco Bieri and Gabor A. Somorjai* Department of Chemistry, University of California, Berkeley, California 94720, and Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 E-mail: somorjai@socrates.berkeley.edu TITLE RUNNING HEAD: Pyrrole hydrogenation over Rh(111) and Pt(111) RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required according to the journal that you are submitting your paper to) CORRESPONDING AUTHOR FOOTNOTE: Gabor A. Somorjai, Tel: 510-642-4053. Fax: 510-643- 9668. E-mail: somorjai@socrates.berkeley.edu. ABSTRACT. Sum frequency generation surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to study the adsorption and hydrogenation of pyrrole over both Pt(111) and Rh(111) single-crystal surfaces at Torr pressures (3 Torr pyrrole, 30 Torr H 2 ) to form pyrrolidine and the minor product butylamine. Over Pt(111) at 298K it was found that pyrrole adsorbs in an upright geometry cleaving the N-H bond to bind through the nitrogen evidenced by SFG data.

Evanescent-wave cavity ring-down spectroscopy was used to monitor the adsorption of human hemoglobin to a fused-silica surface from aqueous solution. An uncoated dove prism was situated in a ring-down cavity such that the beam entered and exited with a normal-incidence geometry. This afforded ring-down times as high as 5 mus and values of sigma(tau)/tau as low as 0.3%. Normal-incidence geometry permits the detection of both S- and P-polarized light, yielding some information of the orientation of adsorbates. The orientation of the adsorbed hemoglobin molecules is found to change as adsorption progresses, but with a different time profile than adsorption itself. The adsorption kinetics from a quiescent solution is consistent with a reaction-diffusion model that includes both reversible and irreversible adsorption operating in parallel. Systems behaving according to this model also seem to display adsorption isotherms, although the increased adsorption from more concentrated solutions is only a consequence of the system being under kinetic control. In some cases, this may be sufficient to explain the paradox of protein adsorption systems which seem to be both irreversible and consistent with isotherm models as well.

Sum frequency generation (SFG) surface vibrational spectroscopy and kinetic measurements using gas chromatography have identified at least two reaction pathways for benzene hydrogenation on the Pt(100) and Pt(111) single-crystal surfaces at Torr pressures. Kinetic studies at low temperatures (310-370 K) show that benzene hydrogenation does not proceed through cyclohexene. A Langmuir-Hinshelwood-type rate law for the low-temperature reaction pathway is identified. The rate-determining step for this pathway is the addition of the first hydrogen atom to adsorbed benzene for both single-crystal surfaces, which is verified by the spectroscopic observation of adsorbed benzene at low temperatures on both the Pt(100) and Pt(111) crystal faces. Low-temperature SFG studies reveal chemisorbed and physisorbed benzene on both surfaces. At higher temperatures (370-440 K), hydrogenation of benzene to pi-allyl c-C(6)H(9) is observed only on the Pt(100) surface. Previous single-crystal studies have identified pi-allyl c-C(6)H(9) as the rate-determining step for cyclohexene hydrogenation to cyclohexane.

Coherent anti-Stokes Raman spectroscopy (CARS) is a sensitive technique for probing highly luminous flames in combustion applications to determine temperatures and species concentrations. CARS thermometry has been demonstrated for the vibrational Q-branch and pure-rotational S-branch of several small molecules. Practical advantages of pure-rotational CARS, such as multi-species detection, reduction of coherent line mixing and collisional narrowing even at high pressures, and the potential for more precise thermometry, have motivated experimental and theoretical advances in S-branch CARS of nitrogen (N2), for example, which is a dominant species in air-fed combustion processes. Although hydrogen (H2) is of interest given its prevalence as a reactant and product in many gas-phase reactions, laser bandwidth limitations have precluded the extension of CARS thermometry to the H2 S-branch. We demonstrate H2 thermometry using hybrid femtosecond/picosecond pure-rotational CARS, in which a broadband pump/Stokes pu...

We develop planar coherent Raman spectroscopy for instantaneous two-dimensional diagnostic imaging in chemically reactive flows. Spatially correlated spectra from N2, O2, and H2 are detected within a single-laser-shot, and temperature contour maps are derived.

We develop a coherent Raman technique for simultaneous planar imaging and multiplex spectroscopy provided in a single-laser-shot. Spatially correlated spectra from multiple species in a two-dimensional field are presented and possible gas-phase applications are discussed.

Single laser pulse methods for 1D and 2D coherent spectral imaging with coherent anti-Stokes Raman spectroscopy have recently been developed for studies of gas phase reacting systems, with particular focus on combustion diagnostics. Article not available.

Advances in technology for electrochemical energy storage require increased understanding of electrolyte/electrode interfaces, including the electric double layer structure, and processes involved in charging of the interface, and the incorporation of this understanding into quantitative models. Simplified models such as Helmholtz's electric double-layer (EDL) concept don't account for the molecular nature of ion distributions, solvents, and electrode surfaces and therefore cannot be used in predictive, high-fidelity simulations for device design. This report presents theoretical results from models that explicitly include the molecular nature of the electrical double layer and predict critical electrochemical quantities such as interfacial capacitance. It also describes development of experimental tools for probing molecular properties of electrochemical interfaces through optical spectroscopy. These optical experimental methods are designed to test our new theoretical models that provide descriptions of the electric double layer in unprecedented detail.

Coherent anti-Stokes Raman spectroscopy (CARS) has been widely used as a powerful tool for chemical sensing, molecular dynamics measurements, and rovibrational spectroscopy since its development over 30 years ago, finding use in fields of study as diverse as combustion diagnostics, cell biology, plasma physics, and the standoff detection of explosives. The capability for acquiring resolved CARS spectra in multiple spatial dimensions within a single laser shot has been a long-standing goal for the study of dynamical processes, but has proven elusive because of both phase-matching and detection considerations. Here, by combining new phase matching and detection schemes with the high efficiency of femtosecond excitation of Raman coherences, we introduce a technique for single-shot two-dimensional (2D) spatial measurements of gas phase CARS spectra. We demonstrate a spectrometer enabling both 2D plane imaging and spectroscopy simultaneously, and present the instantaneous measurement of 15,000 spatially correlated rotational CARS spectra in N2 and air over a 2D field of 40 mm(2).

A hybrid fs/ps pure-rotational CARS scheme is characterized in furnace-heated air at temperatures from 290 to 800 K. Impulsive femtosecond excitation is used to prepare a rotational Raman coherence that is probed with a ps-duration beam generated from an initially broadband fs pulse that is bandwidth limited using air-spaced Fabry-Perot etalons. CARS spectra are generated using 1.5- and 7.0-ps duration probe beams with corresponding coarse and narrow spectral widths. The spectra are fitted using a simple phenomenological model for both shot-averaged and single-shot measurements of temperature and oxygen mole fraction. Our single-shot temperature measurements exhibit high levels of precision and accuracy when the spectrally coarse 1.5-ps probe beam is used, demonstrating that high spectral resolution is not required for thermometry. An initial assessment of concentration measurements in air is also provided, with best results obtained using the higher resolution 7.0-ps probe. This systematic assessment of the hybrid CARS technique demonstrates its utility for practical application in low-temperature gas-phase systems.

A hybrid fs/ps pure-rotational CARS scheme is characterized for thermometry in furnace-heated air at temperatures from 290 to 800 K. Impulsive femtosecond excitation is used to prepare a rotational Raman coherence that is probed with a ps-duration beam generated from an initially broadband fs pulse that is bandwidth limited using air-spaced Fabry-Perot etalons. CARS spectra are generated using 1.5- and 7-ps duration probe beams with corresponding coarse and narrow spectral widths. The spectra are fitted using a simple phenomenological model for both shot-averaged and single-shot measurements of temperature and oxygen mole fraction. Our single-shot measurements exhibit high levels of precision when the spectrally coarse 1.5-ps probe beam is used. This systematic assessment of the hybrid CARS technique demonstrates its utility for practical application in moderatetemperature gas-phase systems.

A counter-propagating beam geometry is employed for high spatial resolution 1D picosecond rotational CARS measurements, allowing for a factor of 10 higher spatial resolution and 102 signal increase over a standard small-angle BOXCARS geometry.

Sum frequency generation surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to systematically study the adsorption and hydrogenation of furan over Pt(111) and Pt(100) single-crystal surfaces and size-controlled 1.0-nm, 3.5-nm and 7.0-nm Pt nanoparticles at Torr pressures (10 Torr of furan, 100 Torr of H(2)) to form dihydrofuran, tetrahydrofuran, and the ring-cracking products butanol and propylene. As determined by SFG, the furan ring lies parallel to all Pt surfaces studied under hydrogenation conditions. Upright THF and the oxametallacycle intermediate are observed over the nanoparticle catalysts under reaction conditions. Butoxy increases in surface concentration over Pt(111) with increasing temperature in agreement with selectivity trends.

In this work we characterize time-resolved pure-rotational CARS using picosecond lasers in combination with data acquisition and evaluation in the frequency-domain. By delaying the probe pulse relative to the pump and Stokes pulses typical drawback of nanosecond pure rotational CARS are prevailed. The results from measurements in a laminar sooting nonpremixed propane flame are compared with those obtained using the commonly applied CARS polarization technique for interference suppression.

Time-resolved picosecond pure-rotational coherent anti-Stokes Raman spectroscopy is applied for thermometry and 1-D imaging in flames. Time-delaying the probe pulse enables successful suppression of unwanted resonant and non-resonant four wave mixing background signals.

Time-resolved picosecond pure-rotational coherent anti-Stokes Raman spectroscopy is demonstrated for thermometry and species concentration determination in flames. Time-delaying the probe pulse enables successful suppression of unwanted signals. A theoretical model is under development.

We propose a technique for ultrabroadband planar coherent Raman spectroscopy that enables wideband chemically selective mapping of molecular partition functions in the gas-phase within a single-laser-shot. A spectral region spanning 0–4200 cm−1 is excited simultaneously, in principle allowing for coherent planar imaging of most all fundamental Raman-active modes. This unique instantaneous and spatially correlated assessment enables multiplexed studies of transient dynamical systems in a two-dimensional (2D) field. Here, we demonstrate single-laser-shot high temperature diagnostics of H2, with spatially resolved 2D measurement of transitions of both the pure-rotational H2 S-branch and the vibrational H2 Q-branch, analyzing the temperature contour of a reacting fuel-species as it evolves at a flame-front.

We propose and develop a method for wideband coherent anti-Stokes Raman spectroscopy (CARS) in the gas phase and demonstrate the single-shot measurement of N2, H2, CO2, O2, and CH4. Pure-rotational and vibrational O-, Q-, and S- branch spectra are collected simultaneously, with high spectral and spatial resolution, and within a single-laser-shot. The relative intensity of the rotational and vibrational signals can be tuned arbitrarily using polarization techniques. The ultrashort 7 fs pump and Stokes pulses are automatically overlapped temporally and spatially using a two-beam CARS technique, and the crossed probe beam allows for excellent spatial sectioning of the probed location.