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.     

Single-Shot Gas-Phase Thermometry by Time-to-Frequency Mapping of Coherence Dephasing

We demonstrate a single-beam coherent anti-Stokes Raman scattering (CARS) technique for gas-phase thermometry that assesses the species-specific local gas temperature by single-shot time-to-frequency mapping of Raman-coherence dephasing. The proof-of-principle experiments are performed with air in a temperature-controlled gas cell. Impulsive excitation of molecular vibrations by an ultrashort pump/Stokes pulse is followed by multipulse probing of the 2330 cm(-1) Raman transition of N(2). This sequence of colored probe pulses, delayed in time with respect to each other and corresponding to three isolated spectral bands, imprints the coherence dephasing onto the measured CARS spectrum. For calibration purposes, the dephasing rates are recorded at various gas temperatures, and the relationship is fitted to a linear regression. The calibration data are then used to determine the gas temperature and are shown to provide better than 15 K accuracy. The described approach is insensitive to pulse energy fluctuations and can, in principle, gauge the temperature of multiple chemical species in a single laser shot, which is deemed particularly valuable for temperature profiling of reacting flows in gas-turbine combustors.     

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.     

Photoluminescence quenching effect on porous silicon films for gas sensors application

Porous silicon (PS) films were investigated by Raman, and photoluminescence (PL) spectroscopies using different laser excitations: 488.0, 514.5, 632.8, and 782.0 nm. The analysis of the first-order and second-order Raman spectra have shown that the band gaps of the PS films are indirect as in the bulk c-Si. The Raman phonon and the PL spectra as well as the spectral distribution of the linear polarisation degree (LPD) of PS layers have shown to be dependent on the laser excitation energy. This dependence cannot be explained within the quantum confinement model. A mechanism for the PL emission in PS layers is presented in which the radiative recombination of electron-hole pairs occurs in localised centres (the Si-O-SiR moieties) at the pore/crystallite interface. These quasi-molecular centres are Jahn-Teller active, i.e. the radiative recombination is a phonon-assisted phenomena. The adsorption of gas molecules on the porous silicon surface was studied throughout photoluminescence quenching effect. The adsorption experiments were performed at 10(-6) bar of pressure using gas molecules of organic solvents. In all these cases, the PL intensity was recovered after gas desorption. The PL quenching effect was explained in the sense of electron transfer mechanism (ET).     

Ultrafast ring opening in 1,3-cyclohexadiene investigated by simplex-based spectral unmixing

We use spectral unmixing to determine the number of transient photoproducts and to track their evolution following the photo-excitation of 1,3-cyclohexadiene (CHD) to form 1,3,5-hexatriene (HT) in the gas phase. The ring opening is initiated with a 266 nm ultraviolet laser pulse and probed via fragmentation with a delayed intense infrared 800 nm laser pulse. The ion time-of-flight (TOF) spectra are analyzed with a simplex-based spectral unmixing technique. We find that at least three independent spectra are needed to model the transient TOF spectra. Guided by mathematical and physical constraints, we decompose the transient TOF spectra into three spectra associated with the presence of CHD, CHD(+), and HT, and show how these three species appear at different times during the ring opening.     

Trace gas detection of molecular hydrogen H(2) by photoacoustic stimulated Raman spectroscopy (PARS)

Photoacoustic stimulated Raman spectroscopy (PARS) has been used for sensitive and selective trace gas detection of molecular hydrogen under ambient conditions. In one experiment, 532 nm output of a seeded pulsed Nd:YAG laser is employed as Raman pump source and a Raman shifter filled with gaseous H(2) to obtain Stokes shifted radiation at 683 nm, suitable to stimulate H(2) Raman detection in a photoacoustic cell. A noise equivalent detection limit of 40 ppm by volume H(2) in 1 atm N(2) is obtained (14 mJ at 532 nm, 18 mJ at 683 nm, 10 Hz repetition rate, 58 s measurement time). Another experiment employs a dye laser for stimulating Raman radiation between 681-684 nm, allowing tuneable PARS. A Gaussian spectral fitting procedure has been applied giving a noise equivalent detection limit of 4.6 ppm by volume H(2) in 1 atm N(2) (35 mJ pulse energy at 532 nm, 45 mJ at 681-684 nm, 10 Hz repetition rate, 256 s measurement time). Spectroscopic detection offers the advantage of high selectivity along with the ability to obtain temperature and dynamic information from the rotational population and a line shape analysis, and also allows the discrimination between ortho- and para-H(2).     

Graphene oxide modifications induced by excimer laser irradiations

The properties of graphene oxide foils were modified by excimer laser irradiation at different fluences and times. The irradiations were performed in air and in vacuum using a pulsed UV laser operating at 248-nm wavelength and 23-ns pulse duration. Measurements of ablation yield, microscope surface morphology and Raman spectroscopy were performed. The residual surface shows a significant oxygen reduction due to the removing of functional oxygen groups, a thickness reduction due to the removal of graphene layers depending on the used laser shots and a presence of defects in the graphene sheets as evident by the Raman spectroscopy investigation.     

Applications of ultrashort shaped pulses in microscopy and for controlling chemical reactions

This article presents a new perspective on laser control based on insights into the effect of spectral phase on nonlinear optical processes. Gaining this understanding requires the systematic evaluation of the molecular response as a function of a series of pre-defined accurately shaped laser pulses. The effort required is rewarded with robust, highly reproducible, results. This approach is illustrated by results on selective two-photon excitation microscopy of biological samples, where higher signal and less photobleaching damage are achieved by accurate phase measurement and elimination of high-order phase distortions from the ultrashort laser pulses. A similar systematic approach applied to laser control of gas phase chemical reactions reveals surprising general trends. Molecular fragmentation pattern is found to be dependent on phase shaping. Differently shaped pulses with similar pulse duration have been found to produce similar fragmentation patterns. This implies that any single parameter that is proportional to the pulse duration, such as second harmonic generation intensity, allows us to predict the molecular fragmentation pattern within the experimental noise. This finding, is illustrated here for a series of isomers. Bond selectivity, coherent photochemistry and their applications are discussed in light of results from these systematic studies.     

Pulse chirp effects in ultrafast laser-induced breakdown spectroscopy

When compared to many other sensitive methods for material detection, such as inductively coupled mass spectroscopy and thermal ionization mass spectroscopy, laser-induced breakdown spectroscopy (LIBS) typically exhibits a lower signal-to-noise ratio (SNR), resulting in higher detection limits. Increasing the SNR of LIBS would improve the ability to characterize the sample composition with increased accuracy and speed and reduce the amount of material needed to perform analysis. We have been investigating the effect of simple ultrashort laser pulse shaping on the SNR of LIBS. Our goal is to control the dynamics of the ionization and recombination processes in the laser-produced plasma to favorably affect the SNR associated with the line emission from the plasma. Pulse shaping is performed using an acousto-optic programmable dispersive filter. An adaptive learning algorithm is being developed to automate the pulse shape optimization process for maximization of LIBS SNR in nuclear security-relevant material characterization scenarios. We report a 27 % increase of the SNR for non-gated LIBS measurements of uranium by utilizing simple pulse shaping limited exclusively to excess quadratic spectral phase of the laser pulse.     

Closed loop coherent control of electronic transitions in gallium arsenide

A genetic algorithm was used to control the photoluminesce-nce (PL) from GaAs(100). A spatial light modulator (SLM) used feedback from the emission to optimize the spectral phase profile of an ultrashort laser pulse. Most of the experiments were performed using a sine phase function to optimize the integrated PL spectrum over a specified wavelength range, with the amplitude and period of the phase function treated as genetic parameters. An order of magnitude increase in signal was achieved after only one generation, and an optimized waveform, consisting of three equally spaced pulses approximately 0.8 ps apart, was obtained after 15 generations. The effects of fluence, polarization, relative phase of the subpulses, and spectral range of the optimized PL were investigated. In addition, preliminary experiments were performed using the phases of individual pixels of the SLM as genetic variables. The PL spectrum is identified with recombination of electron-hole pairs in the L-valley of the Brillouin zone. Control is achieved by coherent manipulation of plasma electrons. It is proposed that hot electrons excite lattice phonons, which in turn scatter carriers into the L-valley.     

Raman, fluorescence, and time-resolved light scattering as optical diagnostic techniques to separate diseased and normal biomedical media.

Studies of Raman scattering, fluorescence and time-resolved light scattering were conducted on cancer and normal biomedical media. Fourier transform Raman spectroscopic measurements were performed on human normal, benign and cancerous tissues from gynecological (GYN) tracts. A comparison of the intensity differences between various Raman modes as well as the number of Raman lines, enables one to distinguish normal GYN tissues from diseased tissues. Fluorescence spectroscopic measurements on human breast tissues show that the ratio of fluorescence intensity at 340 nm to that at 440 nm can be used to distinguish between cancerous and non-cancerous tissues. Separate studies on normal and cancerous breast cell lines show spectral differences. The measurements of back-scattered ultrafast laser pulses from human breast tissues show differences in the scattered pulse profiles for different tissues. These studies show that various optical techniques have the potential to be used in medical diagnostic applications.     

Theory of femtosecond coherent anti-Stokes Raman scattering spectroscopy of gas-phase transitions

A theoretical analysis of coherent anti-Stokes Raman scattering (CARS) spectroscopy of gas-phase resonances using femtosecond lasers is performed. The time-dependent density matrix equations for the femtosecond CARS process are formulated and manipulated into a form suitable for solution by direct numerical integration (DNI). The temporal shapes of the pump, Stokes, and probe laser pulses are specified as an input to the DNI calculations. It is assumed that the laser pulse shapes are 70 fs Gaussians and that the pulses are Fourier-transform limited. A single excited electronic level is defined as an effective intermediate level in the Raman process, and transition strengths are adjusted to match the experimental Raman polarizability. The excitation of the Raman coherence is investigated for different Q-branch rotational transitions in the fundamental 2330 cm(-1) band of diatomic nitrogen, assuming that the pump and Stokes pulses are temporally overlapped. The excitation process is shown to be virtually identical for transitions ranging from Q2 to Q20. The excitation of the Raman coherences is also very efficient; for laser irradiances of 5x10(17) W/m2, corresponding approximately to a 100 microJ, 70 fs pulse focused to 50 microm, approximately 10% of the population of the ground Raman level is pumped to the excited Raman level during the impulsive pump-Stokes excitation, and the magnitude of the induced Raman coherence reaches 40% of its maximum possible value. The theoretical results are compared with the results of experiments where the femtosecond CARS signal is recorded as a function of probe delay with respect to the impulsive pump-Stokes excitation.     

Cavity-enhanced Raman spectroscopy with optical feedback cw diode lasers for gas phase analysis and spectroscopy

A variant of cavity-enhanced Raman spectroscopy (CERS) is introduced, in which diode laser radiation at 635 nm is coupled into an external linear optical cavity composed of two highly reflective mirrors. Using optical feedback stabilisation, build-up of circulating laser power by 3 orders of magnitude occurs. Strong Raman signals are collected in forward scattering geometry. Gas phase CERS spectra of H(2), air, CH(4) and benzene are recorded to demonstrate the potential for analytical applications and fundamental molecular studies. Noise equivalent limits of detection in the ppm by volume range (1 bar sample) can be achieved with excellent linearity with a 10 mW excitation laser, with sensitivity increasing with laser power and integration time. The apparatus can be operated with battery powered components and can thus be very compact and portable. Possible applications include safety monitoring of hydrogen gas levels, isotope tracer studies (e.g., (14)N/(15)N ratios), observing isotopomers of hydrogen (e.g., radioactive tritium), and simultaneous multi-component gas analysis. CERS has the potential to become a standard method for sensitive gas phase Raman spectroscopy.     

Mass spectrometry of intact neutral macromolecules using intense non‐resonant femtosecond laser vaporization with electrospray post‐ionization

Intact, nonvolatile, biological macromolecules can be transferred directly from the solid state into the gas phase, in ambient air, for subsequent mass spectral analysis using non‐resonant femtosecond (fs) laser desorption combined with electrospray ionization (ESI). Mass spectral measurements for neat samples, including a dipeptide, protoporphyrin IX and vitamin B12 adsorbed on a glass insulating surface, were obtained using an 800 nm, 70 fs laser with an intensity of 10¹³ W cm⁻². No appreciable signal was detected when atmospheric matrix‐assisted or neat (matrix‐free) fs laser desorption was performed without ESI, indicating neutral desorption. Copyright © 2009 John Wiley & Sons, Ltd.     

Efficient Preparation of D2 Molecules in v=2 by Stimulated Raman Pumping

We report the preparation of D₂ molecules in v=2 level in molecular beam condition. A single longitudinal mode laser system was used for excitation of D₂ from (v=0, j=0) to (v=2, j=0) with the scheme of stimulated Raman pumping. An excitation efficiency of 25.2% has been achieved, which was determined by the scheme of resonance-enhanced multiphoton ionization. Dependence of relative excitation efficiency on laser energy has been measured. We found that the increasing rate of excitation efficiency became slower as pulse energy of Stokes laser increase, while the excitation efficiency still increases approximately linearly with pump pulse energies up to 60 mJ. The spectral line shapes of Raman transition was also measured at different laser energies and considerable dynamical Stark effect was observed. A single peak was found on the three dimension surface of relative excitation efficiency, indicating the process occurred in the present study is a process of stimulated Raman pumping instead of stimulated adiabatic Raman passage.     

Joint analyses by laser-induced breakdown spectroscopy (LIBS) and Raman spectroscopy at stand-off distances

Raman spectroscopy and laser-induced breakdown spectroscopy (LIBS) of solid samples have both been shown to be feasible with sample-to-instrument distances of many meters. The two techniques are very useful together, as the combination of elemental compositions from LIBS and molecular vibrational information from Raman spectroscopy strongly complement each other. Remote LIBS and Raman spectroscopy spectra were taken together on a number of mineral samples including sulfates, carbonates and silicates at a distance of 8.3 m. The complementary nature of these spectra is highlighted and discussed. A factor of approximately 20 difference in intensity was observed between the brightest Raman line of calcite, at optimal laser power, and the brighter Ca I LIBS emission line measured with 55 mJ/pulse laser power. LIBS and Raman spectroscopy have several obstacles to devising a single instrument capable of both techniques. These include the differing spectral ranges and required detection sensitivity. The current state of technology in these areas is discussed.     

Transmission Raman measurement directly through packed corn kernels to improve sample representation and accuracy of compositional analysis

The potential of transmission Raman spectroscopy for direct analysis of packed granular samples, one of the most frequently encountered sample types in the field of non-destructive spectroscopic analysis, has been evaluated. For this purpose, transmission Raman spectra were collected by laser illumination through packed corn kernels to determine their protein concentration. Back-scattering Raman spectra of the same samples were also collected for comparison. Raman spectral features of the major kernel constituents were initially characterized, and Raman mapping over the whole kernel face was performed to investigate the inhomogeneous distribution of constituents in a kernel. Possible variations of transmission spectral features depending on the laser illumination on different locations of a kernel were investigated, since the orientation of kernels in the packing was essentially random. Rotation of kernel packing during spectral collection was helpful in improving the compositional representation of packed kernels. With partial least squares (PLS) regression, the protein concentrations were determined using both spectral collection methods and the resulting accuracies were compared. As a result, the transmission measurement provided a more accurate determination of protein concentration since it enabled deeper sampling across the packed kernels, leading to a better compositional representation of them. By contrast, in the back-scattering measurement, kernels on the top of the packing were mainly sampled for the spectral acquisition. Moreover, the back-scattering spectral feature, more weighted to constituents localized at the outer portion of a kernel, was short of representing the overall composition of a kernel.     

Coherent anti-Stokes Raman scattering: Spectroscopy and microscopy

In this review the basis, recent developments and applications of coherent anti-Stokes Raman scattering (CARS) in the fields of spectroscopy and microscopy are dialed with. The nonlinear susceptibility of the investigated molecule induced by pump and Stokes laser beams employed in the CARS technique is discussed. The relation between the nonlinear susceptibility, the different CARS laser intensities and the phase matching condition between them is also presented. The structure of CARS spectrum is analyzed as a function of the physical characteristics of the different employed lasers. This includes laser half widths, interference effects, cross-coherence and saturation of the resultant CARS signal by stimulated Raman scatter process (SRS). The different broadening mechanisms for CARS spectral line such as pressure and Doppler broadening are demonstrated. The recent progress in CARS for the in situ reaction flame diagnosis due to its suitability for detection of vibrational-rotational excited gas molecules present in the electronic ground state is discussed. CARS diagnosis for liquid- and solid-phases including the progress in polymeric materials is considered. The applications of CARS microscopy are reviewed in the view of its recent advances to study chemical and biological systems.     

A new non-invasive, quantitative Raman technique for the determination of an active ingredient in pharmaceutical liquids by direct measurement through a plastic bottle

The concentration of an active pharmaceutical ingredient (povidone) in a commercial eyewash solution has been measured directly through a plastic (low-density polyethylene: LDPE) container using a wide area illumination (WAI) Raman scheme. The WAI scheme allows excitation using a 6 mm laser spot (focal length: 248 mm) that is designed to cover a wide sample area. As a result, it has the potential to improve the reliability Raman measurements by significantly enhancing representative sample interrogation, thus improving the reproducibility of sampling. It also decreases the sensitivity of sample placement with regard to the excitation focal plane. Simultaneously, isobutyric anhydride was placed in front of the bottles to use for a synchronous external standard configuration. This helps to correct the problematic variation of Raman intensity from the inherent fluctuation in laser power. Using the WAI Raman scheme combined with the synchronous standard method, the povidone concentration was successfully measured with spectral collection that was performed through a plastic barrier. The conventional Raman scheme was difficult to employ for the same purpose because of the degraded spectral reproducibility resulting from the smaller laser illumination area and the sensitivity of such an approach to the position of the sample bottle. The result from this study suggests that the WAI scheme exhibits a strong potential for the non-destructive quantitative analysis of pharmaceuticals measured directly in plastic containers. Preliminary work also shows that similar measurements can also be made in glass bottles. If implemented, this technique could be utilized as a simple and rugged method for quality assurance of final products in a manner consistent with Process analytical technology (PAT) requirements.     

CN emission spectroscopy study of carbon plasma in nitrogen environment

Spectroscopic emission diagnostics of a carbon plasma created by an excimer KrF laser pulse at three laser fluences (12, 25 and 32 J/cm²) is performed under nitrogen ambient at pressures of 0.5 and 1 mbar. By following the time evolution of the radical CN spectral emission profiles, we notice, at a certain distance from the target surface, the existence of twin peaks for the time of flight distribution. This double structure depends on laser fluence and gas pressure parameters. The first peak moves forward in relation with the plasma expansion whereas the second peak moves backward and it is attributed to CN species undergoing oscillations or reflected shocks.