We demonstrate a single-beam, standoff (>10m) coherent anti-Stokes Raman scattering spectroscopy (CARS) of various materials, including trace amounts of explosives and nitrate samples, under ambient light conditions. The multiplex measurement of characteristic molecular vibrations with <20cm-1 spectral resolution is carried out using a single broadband (>550cm-1) phase-shaped femtosecond laser pulse. We exploit the strong nonresonant background signal for amplification of the weak backscattered resonant CARS signal by using a homodyne detection scheme. This facilitates a simple, highly sensitive single-beam spectroscopic technique, with a potential for hazardous materials standoff detection applications.
We demonstrate single-beam coherent anti-Stokes Raman spectroscopy (CARS), for detecting and identifying traces of solids, including minute amounts of explosives, from a standoff distance (>50 m) using intense femtosecond pulses. Until now, single-beam CARS methods relied on pulse-shapers in order to obtain vibrational spectra. Here we present a simple and easy-to-implement detection scheme, using a commercially available notch filter, that does not require the use of a pulse-shaper.
Spectral compression of femtosecond pulses by second harmonic generation in the presence of substantial group velocity dispersion provides a convenient source of narrowband Raman pump pulses for femtosecond stimulated Raman spectroscopy (FSRS). We discuss here a simple and efficient modification that dramatically increases the versatility of the second harmonic spectral compression technique. Adding a spectral filter following second harmonic generation produces narrowband pulses with a superior temporal profile. This simple modification i) increases the Raman gain for a given pulse energy, ii…
We report on experimental realization of impulsive rotational Raman scattering from neutral nitrogen molecules in a femtosecond laser filament using an intense self-induced white-light seeding "air laser" generated during the filamentation of an 800 nm Ti: Sapphire laser in nitrogen gas. The impulsive rotational Raman fingerprint signals are observed with a maximum conversion efficiency of ~0.8%. Our observation provides a promising way of remote identification and location of chemical species in atmosphere by rotational Raman scattering of molecules.
Understanding the physical mechanisms of the refractive index modulation induced by femtosecond laser writing is crucial for tailoring the properties of the resulting optical waveguides. In this work we apply polarized Raman spectroscopy to study the origin of stress-induced waveguides in diamond, produced by femtosecond laser writing. The change in the refractive index induced by the femtosecond laser in the crystal is derived from the measured stress in the waveguides. The results help to explain the waveguide polarization sensitive guiding mechanism, as well as providing a technique for the…
We report on the generation of broadband, high-energy femtosecond pulses centered at 1.28 um by stimulated Raman scattering in pressurized hydrogen cell. Stimulated Raman scattering is performed by two chirped and delayed pulses originating from a multi-mJ Ti:Sapphire amplifier. The Stokes pulse carries energy of 4.4 mJ and is recompressed down to 66 fs by reflective grating pair. We characterized the short-wavelength mid-infrared source in view of energy stability, beam profile and conversion efficiency at a repetition rate of 100 Hz and 10 Hz. The demonstrated laser will benefit intense THz …
We report generation of cascaded rotational Raman scattering up to 58th orders in coherently excited CO_2 molecules. The high-order Raman scattering, which produces a quasiperiodic frequency comb with more than 600 sidebands, is obtained using an intense femtosecond laser to impulsively excite rotational coherence and the femtosecond-laser-induced N_2^+ lasing to generate cascaded Raman signals. The novel configuration allows this experiment to be performed with a single femtosecond laser beam at free-space standoff locations. It is revealed that the efficient spectral extension of Raman signa…
Spatial phase coherence in femtosecond coherent Raman scattering
RWTH Aachen University（亚琛工业大学）；ENEA（意大利国家新能源与可再生能源研究中心）；Università di Roma “La Sapienza”（罗马大学）；Lund University（隆德大学）；The University of Edinburgh（爱丁堡大学）
We exploit inverse Raman scattering and solvated electron absorption to perform a quantitative characterization of the energy loss and ionization dynamics in water with tightly focused near-infrared femtosecond pulses. A comparison between experimental data and numerical simulations suggests that the ionization energy of water is 8 eV, rather than the commonly used value of 6.5 eV. We also introduce an equation for the Raman gain valid for ultra-short pulses that validates our experimental procedure.
We demonstrate a novel technique of coherent Raman spectroscopy with a femtosecond laser. We apply to a molecular sample a sequence of pairs of ultrashort excitation and probe pulses, with a linearly increasing time delay between the two pulses from one pair to the next. We measure, as a function of the delay, the intensity modulation in the signal resulting from the differential detection of the Stokes and anti-Stokes radiations generated at the sample. The Fourier transform of such time-domain signal reveals the spectrum of the excited vibrational Raman transitions. The experimental proof-of…
Raman spectroscopic characterization of crater walls formed upon single-shot high energy femtosecond laser irradiation of dimethacrylate polymer doped with plasmonic gold nanorods
We report on the first demonstration of nonlinear dual-frequency-comb spectroscopy. In multi-heterodyne femtosecond Raman-induced Kerr-effect spectroscopy, the Raman gain resulting from the coherent excitation of molecular vibrations by a spectrally-narrow pump is imprinted onto the femtosecond laser frequency comb probe spectrum. The birefringence signal induced by the nonlinear interaction of these beams and the sample is heterodyned against a frequency comb local oscillator with a repetition frequency slightly different from that of the comb probe. Such time-domain interference provides mul…
Time-resolved femtosecond stimulated Raman spectroscopy (FSRS) is a powerful tool for investigating ultrafast structural and vibrational dynamics in light absorbing systems. However, the technique generally requires exposing a sample to high laser pulse fluences and long acquisition times to achieve adequate signal-to-noise ratios. Here, we describe a timeresolved FSRS instrument built around a Yb ultrafast amplifier operating at 200 kHz, and address some of the unique challenges that arise at high repetition-rates. The setup includes detection with a 9 kHz CMOS camera and an improved dual-cho…
The hybrid Stimulated Raman Scattering - Two Plasmon Decay instability had shown to play the dominant role for plasma waves excitation and energy absorption at interaction of very intense femtosecond obliquely incident $p$-polarized laser pulse (intensity $10^{17}-5\cdot10^{19}$ W/cm$^2$) with a steep gradient ($L\sim λ$) plasma near the quarter critical surface, i.e. within the typical for modern experiments conditions. The plasmons are excited as two wave packets confined near this surface with very wide $\approx ω_0/c$ spatial spectra along its normal. Hence, phase matching conditions for 3…
Electron and vibrational dynamics of molecules are commonly studied by subjecting them to two interactions with a fast actinic pulse that prepares them in a nonstationary state and after a variable delay period $T$, probing them with a Raman process induced by a combination of a broadband and a narrowband pulse. This technique known as femtosecond stimulated Raman spectroscopy (FSRS) can effectively probe time resolved vibrational resonances. We show how FSRS signals can be modeled and interpreted using the stochastic Liouville equations (SLE) originally developed for NMR lineshapes. The SLE p…
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 nitrogen 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 pr…
Excited-state vibrations are crucial for determining photophysical and photochemical properties of molecular compounds. Stimulated Raman scattering can coherently stimulate and probe molecular vibrations with optical pulses, but it is generally restricted to ground state properties. Working in resonance conditions, indeed, enables cross-section enhancement and selective excitation to a targeted electronic level, but is hampered by an increased signal complexity due to the presence of overlapping spectral contributions. Here, we show how detailed information on ground and excited state vibratio…
We explore parabolic pre-shaping as a means of generating and amplifying ultrashort pulses. We develop a theoretical framework for modeling the technique and use its conclusions to design a femtosecond fiber amplifier. Starting from 9 ps pulses, we obtain 4.3 $μ$J, nearly transform-limited pulses 275 fs in duration, simultaneously achieving over 40 dB gain and 33-fold compression. Finally, we show that this amplification scheme is limited by Raman scattering, and outline a method by which the pulse duration and energy may be further improved and tailored for a given application.
Collection of weak signals from remote locations is the primary goal and the primary hurdle of optical stand-off detection schemes. Typically, the measured signal is enhanced using large numerical aperture collection optics and high gain detectors. We show that the signal in remote detection techniques can be enhanced by using a long-lived air waveguide generated by an array of femtosecond filaments. We present a proof of principle experiment using an air plasma spark source and a ~1 m air waveguide showing an increase in collected signal of ~50%. For standoff distances of 100 m, this implies …
Single-shot time resolved Coherent Anti-Stokes Raman Scattering (CARS) is presented as a viable method for fast measurements of molecular spectra. The method is based on the short spatial extension of femtosecond pulses and maps time delays between pulses onto the region of intersection between broad beams. The image of the emitted CARS signal contains full temporal information on the field-free molecular dynamics, from which spectral information is extracted. The method is demonstrated on liquid samples of CHBr3 and CHCl3 and the Raman spectrum of the low-lying vibrational states of these mol…
We investigate the prospects of creating broad rotational wave packets by means of molecular interaction with long sequences of intense femtosecond pulses. Using state-resolved rotational Raman spectroscopy of oxygen, subject to a sequence of more than 20 laser pulses with peak intensities exceeding $10^{13}$ W/cm$^{2}$ per pulse, we show that the centrifugal distortion is the main obstacle on the way to reaching high rotational states. We demonstrate that the timing of the pulses can be optimized to partially mitigate the centrifugal limit. The cumulative effect of a long pulse sequence resul…
Multiphoton microscopy has enabled us to image cellular dynamics in vivo. However, the excitation wavelength for imaging with commercially available lasers is mostly limited between 650-1040 nm. Here we develop a femtosecond fiber laser system that produces $\sim$150 fs pulses at 1.8 $μ$m. Our system starts from an erbium-doped silica fiber laser, and its wavelength is converted to 1.8 $μ$m using a Raman shift fiber. The 1.8 $μ$m pulses are amplified with a two-stage Tm:ZBLAN fiber amplifier. The final pulse energy is $\sim$1 $μ$J, sufficient for in vivo imaging.
Generation of high-repetition-rate, femtosecond, soliton pulse trains through dual-wavelength pumping of a dispersion-decreasing fiber is studied numerically. The achievable shortest pulse width is found to be limited by third-order dispersion that has a significant effect on the pulse-compression dynamics. The output wavelength is red shifted because of intrapulse Raman scattering and depends heavily on third-order dispersion, whose positive values lead to the most red shifted solitons (>25% of the input pump center wavelength). The proposed scheme allows the generation of ultrashort pulse tr…
This work investigates the utility of femtosecond pulse shaping in increasing the efficiency of Raman excitation of molecules in the strong-field interaction regime. We study experimentally and theoretically the effect of pulse shaping on the strength of non-resonant coherent anti-Stokes Raman scattering in iodine vapor at laser intensities exceeding $10^{13}$ W/cm$^2$. We show that unlike the perturbative case, shaping strong non-resonant laser pulses can increase the signal strength beyond that observed with the transform-limited excitation. Both adiabatic and non-adiabatic schemes of excita…
The four-wave mixing produced with two ultrashort phase-locked w-3w laser pulses propagating coherently in a two-level system in the infrared spectral region is shown to depend on the pulses relative phase. The Maxwell-Bloch equations are solved beyond the rotating-wave approximation to account for field frequencies which are largely detuned from the atomic resonance. The relative phase dominating the efficiency of the coupling to the 5w anti-Stokes Raman component is determined by sign of the total ac Stark shift induced in the system, in such a way that the phase influence disappears precise…
We present a simple method and its experimental implementation to completely determine the characteristics of the pump-and-probe pulse and the Stokes pulse in a coherent anti-Stokes Raman scattering microscope at sample level without additional autocorrelators. Our approach exploits the delay line, ubiquitous in such microscopes, to perform a convolution of the pump-and-probe and Stokes pulses as a function of their relative delay and it is based on the detection of the photons emitted from an appropriate non-linear sample. The analysis of the non-resonant four-wave-mixing and sum-frequency-ge…
This letter is to pave the way towards the demonstration of spatiotemporal similariton pulses evolution in passive multimode fibers with Raman amplification. We present numerically these issues in a graded-index and step-index multimode fibers and provide a first look at the complex spatiotemporal dynamics of similariton pulses. The results showed that the similariton pulses can be generated in both multimode fibers. The temporal and the spectral evolution of the pulses can be characterized as parabolic shapes with linear chirp and kW peak power. By compressed these, high energy femtoseconds p…
High quality lithium niobate thin film microresonators provide an ideal platform for on-chip nonlinear optics applications. However, the phase matching condition for efficient parametric process sets a high requirement for fabrication control. Here we demonstrate a photonic molecular structure composed of two strongly coupled lithium niobate microdisks of different diameters fabricated using femtosecond laser micromachining and focused ion beam milling. With a continuous wave excitation, rich nonlinear optical processes including cascaded four-wave mixing and stimulated Raman scattering were o…
We demonstrate the acquisition of stimulated Raman scattering spectra with the use of a single femtosecond pulse. High resolution vibrational spectra are obtained by shifting the phase of a narrow band of frequencies in the broadband input pulse spectrum, using spectral shaping. The vibrational spectrum is resolved by examining the amplitude features formed in the spectrum after interaction with the sample. Using this technique, low frequency Raman lines (<100cm^-1) are resolved in a straightforward manner.
We study the response of graphene to high-intensity 10^11-10^12 Wcm^-2, 50-femtosecond laser pulse excitation. We establish that graphene has a fairly high (~3\times10^12Wcm^-2) single-shot damage threshold. Above this threshold, a single laser pulse cleanly ablates graphene, leaving microscopically defined edges. Below this threshold, we observe laser-induced defect formation that leads to degradation of the lattice over multiple exposures. We identify the lattice modification processes through in-situ Raman microscopy. The effective lifetime of CVD graphene under femtosecond near-IR irradiat…
We report a novel source of twin beams based on modulational instability in high-pressure argon-filled hollow-core kagomé-style photonic-crystal fibre. The source is Raman-free and manifests strong photon-number correlations for femtosecond pulses of squeezed vacuum with a record brightness of ~2500 photons per mode. The ultra-broadband (~50 THz) twin beams are frequency tunable and contain one spatial and less than 5 frequency modes.
The success of non-linear optics relies largely on pulse-to-pulse consistency. In contrast, covariance based techniques used in photoionization electron spectroscopy and mass spectrometry have shown that wealth of information can be extracted from noise that is lost when averaging multiple measurements. Here, we apply covariance based detection to nonlinear optical spectroscopy, and show that noise in a femtosecond laser is not necessarily a liability to be mitigated, but can act as a unique and powerful asset. As a proof of principle we apply this approach to the process of stimulated Raman s…
The effect of femtosecond laser irradiation on bulk and single-layer MoS2 on silicon oxide is studied. Optical, Field Emission Scanning Electron Microscopy (FESEM) and Raman microscopies were used to quantify the damage. The intensity of A1g and E2g1 vibrational modes was recorded as a function of the number of irradiation pulses. The observed behavior was attributed to laser-induced bond breaking and subsequent atoms removal due to electronic excitations. The single-pulse optical damage threshold was determined for the monolayer and bulk under 800nm and 1030nm pulsed laser irradiation and the…
We extend the technique of multiplex coherent Raman spectroscopy with two femtosecond mode-locked lasers to oscillators of a pulse repetition frequency of 1 GHz. We demonstrate spectra of liquids, which span 1100 cm$^{-1}$ of Raman shifts. At a resolution of 6 cm$^{-1}$, their measurement time may be as short as 5 microseconds for a refresh rate of 2 kHz. The waiting period between acquisitions is improved ten-fold compared to previous experiments with two lasers of 100-MHz repetition frequencies.
Optical spectroscopy with broadband femtosecond laser pulses often involves simultaneous excitation of multiple molecular species with close resonance frequencies. Interpreting the collective optical response from molecular mixtures typically requires Fourier analysis of the detected time-resolved signal. We propose an alternative method of separating coherent optical responses from two molecular species with neighboring excitation resonances (here, vibrational modes of oxygen and carbon dioxide). We utilize ro-vibrational coupling as a mechanism of suppressing the strong vibrational response …
Tightly focused femtosecond laser-beam in the non-ablative regime can induce a shock-wave enough to reach locally pressures in the giga-Pascal range or more. In a single beam configuration, the location of the highest-pressure zone is nested within the laser-focus zone, making it difficult to differentiate the effect of the shock-wave pressure from photo-induced and plasma relaxation effect. To circumvent this difficulty, we consider two spatially separated focused beams that individually act as quasi-simultaneous pressure-wave emitters. The zone where both shock-waves interfere constructively…
A number of factors that influence spectral position of the femtosecond pulse in a Kerr-lens modelocked Cr:LiSGaF laser have been identified: high-order dispersion, gain saturation, reabsorption from the ground state, and stimulated Raman scattering. Using the one-dimensional numerical model for the simulation of the laser cavity, the relative contributions of different factors have been compared. The Raman effect provides the largest self-frequency shift from the gain peak (up to 60 nm), followed by the gain saturation (25 nm), while the high-order dispersion contribution is insignificant (5 …
Spintronics is postulated on the possibility to employ the magnetic degree of freedom of electrons for computation and couple it to charges. In this view, the combination of the high-frequency of spin manipulations offered by antiferromagnets, with the wide tunability of the electronic properties peculiar of semiconductors provides a promising and intriguing platform. Here we explore this scenario in $α$-MnTe, which is a semiconductor antiferromagnetically ordered at room temperature. Relying on a Raman mechanism and femtosecond laser pulses, we drive degenerate modes of coherent optical phono…
The output pulses of a commercial high-power femtosecond fiber laser or amplifier are typically around 300-500 fs with a wavelength around 1030 nm and 10s of $μ$J pulse energy. Here we present a numerical study of cascaded quadratic soliton compression of such pulses in LiNbO$_3$ using a type I phase matching configuration. We find that because of competing cubic material nonlinearities compression can only occur in the nonstationary regime, where group-velocity mismatch induced Raman-like nonlocal effects prevent compression to below 100 fs. However, the strong group velocity dispersion impli…
The first step in the coherent control of a photoinduced binary reaction is bond making or photoassociation. We have recently demonstrated coherent control of bond making in multi-photon femtosecond photoassociation of hot magnesium atoms, using linearly chirped pulses [Levin et al., arXiv:1411.1542]. The detected yield of photoassociated magnesium dimers was enhanced by positively chirped pulses which is explained theoretically by a combination of purification and chirp-dependent Raman transitions. The yield could be further enhanced by pulse optimization resulting in pulses with an effective…
We propose a novel femtosecond stimulated Raman spectroscopy (FSRS) technique that combines entangled photons with interference detection to select matter pathways and enhance the resolution. Following photo excitation by an actinic pump, the measurement uses a pair of broadband entangled photons, one (signal) interacts with the molecule together with a third narrowband pulse induces the Raman process. The other (idler) photon provides a reference for the coincidence measurement. This interferometric photon-coincidence counting detection allows to separately measure Raman gain and loss signals…
A theoretical investigation on the quantum control of optical coherent four-wave mixing interactions in two-level systems driven by two intense synchronized femtosecond laser pulses of central angular frequencies $ω$ and $3ω$ is reported. By numerically solving the full Maxwell-Bloch equations beyond the slowly-varying envelope and rotating-wave approximations in the time domain, the nonlinear coupling to the optical field at frequency $5ω$ is found to depend critically on the initial relative phase $ϕ$ of the two propagating pulses; the coupling is enhanced when the pulses interfere construct…
We study the spatio-temporal instability generated by a universal unstable attractor in normal dispersion graded-index multimode fiber (GRIN MMF) for femtosecond pulses. Our results present the generation of geometric parametric instability (GPI) sidebands with ultrashort input pulse for the first time. Observed GPI sidebands are 91 THz detuned from the pump wavelength, 800 nm. Detailed analysis carried out numerically by employing coupled-mode pulse propagation model including optical shock and Raman nonlinearity terms. A simplified theoretical model and numerically calculated spectra are wel…
Femtosecond micromachining offers a contact-free and mask-less technique for material patterning. With ultrafast laser irradiation, permanent modifications to the properties of single layer graphene through material ablation or defect introduction can be induced. Multiple femtosecond pulse interactions with a single layer graphene are studied and a low laser ablation threshold ~9.2 mJ/cm2 is reported for a 15 second illumination time. Clean ablated structures are generated in such a multi pulse irradiation configuration at low pulse energies as an attractive alternative to ablation with single…
Using femtosecond laser machining, we have fabricated photonic bandgap materials that influence propagation of phonon-polaritons in ferroelectric crystals. Broadband polaritons were generated with impulsive stimulated Raman scattering (ISRS) using an ultrashort laser pulse, and the spatial and temporal evolution of the polaritons were imaged as they propagated through the fabricated structures with polariton real-space imaging. These techniques offer a new approach to optical materials design.
A possibility to greatly enhance frequency-conversion efficiency of stimulated Raman scattering is shown by making use of extraordinary properties of three-wave mixing of ordinary and backward waves. Such processes are commonly attributed to negative-index plasmonic metamaterials. This work demonstrates the possibility to replace such metamaterials that are very challenging to engineer by readily available crystals which support elastic waves with contra-directed phase and group velocities. The main goal of this work is to investigate specific properties of indicated nonlinear optical process …
Linear off-resonant X-ray Raman techniques are capable of detecting the ultrafast electronic coherences generated when a photoexcited wave packet passes through a conical intersection. A hybrid femtosecond or attosecond probe pulse is employed to excite the system and stimulate the emission of the signal photon, where both fields are components of a hybrid pulse scheme. In this paper, we investigate how attosecond pulse trains, as provided by high-harmonic generation processes, perform as probe pulses in the framework of this spectroscopic technique, instead of single Gaussian pulses. We explo…
We present a general and highly efficient scheme for performing narrow-band Raman transitions between molecular vibrational levels using a coherent train of weak pump-dump pairs of shaped ultrashort pulses. The use of weak pulses permits an analytic description within the framework of coherent control in the perturbative regime, while coherent accumulation of many pulse pairs enables near unity transfer efficiency with a high spectral selectivity, thus forming a powerful combination of pump-dump control schemes and the precision of the frequency comb. The concept is presented analytically and …
Coherent anti-Stokes Raman scattering (CARS) and, in particular, femtosecond adaptive spectroscopic techniques (FAST CARS) have been successfully used for molecular spectroscopy and microscopic imaging. Recent progress in ultrafast nanooptics provides flexibility in generation and control of optical near fields, and holds promise to extend CARS techniques to the nanoscale. In this theoretical study, we demonstrate ultrafast subwavelentgh control of coherent Raman spectra of molecules in the vicinity of a plasmonic nanostructure excited by ultrashort laser pulses. The simulated nanostructure de…
Since its first demonstration in the sixties, coherent anti-Stokes Raman scattering (CARS) has become a powerful spectroscopic sensing tool with broad applications in biology and chemistry. However, it is a complex nonlinear optical process that often leads to the lacks of quantitative data outputs. In this letter, we observe how CARS signal builds up gradually and demonstrate how to control its deferral with laser-pulse shaping. A time-resolved three-color CARS that involves a pair of driving broadband femtosecond pulses and delayed shaped probe pulse is realized experimentally. Driving pulse…
We theoretically and numerically study the influence of both instantaneous and Raman-delayed Kerr nonlinearities as well as a long-wavelength pump in the terahertz (THz) emissions produced by two-color femtosecond filaments in air. Although the Raman-delayed nonlinearity induced by air molecules weakens THz generation, four-wave mixing is found to impact the THz spectra accumulated upon propagation via self-, cross-phase modulations and self-steepening. Besides, using the local current theory, we show that the scaling of laser-to-THz conversion efficiency with the fundamental laser wavelength …
We have applied femtosecond pump-probe technique with variable pump wavelength to study coherent lattice dynamics in Bi single crystal. Comparison of the coherent amplitude as a function of pump photon energy for two different in symmetry Eg and A1g phonon modes with respective spontaneous resonance Raman profiles reveals that their generation mechanisms are quite distinct. We show that displacive excitation, which is the main mechanism for the generation of coherent A1g phonons, cannot be reduced to the Raman scattering responsible for the generation of lower symmetry coherent lattice modes
