High-spectral-resolution coherent anti-Stokes Raman scattering with interferometrically detected broadband chirped pulses

To achieve high-spectral-resolution multiplex coherent anti-Stokes Raman scattering (CARS), one typically uses a narrowband pump pulse and a broadband Stokes pulse. This is to ensure a correspondence between anti-Stokes and vibrational frequencies. We obtain high-resolution CARS spectra of isopropanol, using a broadband chirped pump pulse and a broadband Stokes pulse, by detecting the anti-Stokes pulse with spectral interferometry. With the temporally resolved anti-Stokes signal, we can remove the chirp of the anti-Stokes pulse and restore high spectral resolution while also rejecting nonresonant scattering.     

Two‐beam multiplexed CARS based on a broadband oscillator

A two‐beam multiplexed coherent anti‐Stokes Raman scattering (CARS) microscopy setup is demonstrated by using a broadband (BB) Ti:sapphire oscillator without using any specialty fibres. A well‐defined spectral structure of the source leads to a delay‐sensitive CARS measurement in two‐colour CARS and also provides an efficient means of obtaining three‐colour CARS signals combined with the dispersion compensation of the BB pulse. Our result implies that the background suppression is limited by the onset of the spurious signals caused by the different CARS process, qualitatively differing from what is typically observed in the CARS microscopy. Copyright © 2010 John Wiley & Sons, Ltd.     

Test of an optical parametric oscillator (OPO) as a compact and fast tunable stokes source in coherent anti-stokes raman spectroscopy (CARS)

An optical parametric oscillator (OPO), as a novel kind of broadband Stokes source, is employed for coherent anti-Stokes Raman spectroscopy (CARS). Compared to the conventional dye laser configuration OPO-CARS offers practical advantages. The tunable OPO allows a fast and comfortable frequency tuning. The excitation bandwidth of about 35 cm^–1 (FWHM) limits the spectral range of effective and stable single pulse CARS generation but can be used to enhance selected spectral structures.     

Detecting lateral interfaces with focus‐engineered coherent anti‐Stokes Raman scattering microscopy

Focus‐engineered coherent anti‐Stokes Raman scattering (FE‐CARS) microscopy is used to highlight the lateral interfaces between chemically distinct media. Interface highlighting is achieved by using a HG10 mode for the Stokes laser beam and a HG00 mode for the pump laser beam in the forward detection scheme. The spectral and the orientation dependence of FE‐CARS are found to be in agreement with theoretical predictions. A brief discussion on the relevance of this technique for imaging third‐order nonlinear susceptibility interfaces in thin samples of biological or chemical importance is presented. Copyright © 2008 John Wiley & Sons, Ltd.     

Ultrabroadband single-pulse CARS of liquids using a spatially dispersive Stokes beam

A double-channel spectrometer, which enables to acquire ultrabroadband single-pulse spectra of liquids by Coherent Anti-Stokes Raman Spectroscopy (CARS), is described. The method used to fulfill the phase-matching condition is based on the fact that the CARS efficiency in dispersive media is the largest when the interactive waves cross each other under frequency-determined angles. The dependence of the spatial separation between the pump and Stokes beam, in front of the crossing CARS lens, due to their frequency difference is analysed. It is shown that the different spectral components of an ultrabroadband Stokes source have phase-matched the CARS process when they are laterally shifted by a conjugated prism pair and focused into the sample. The method is tested in the spectral region 2800–3800 cm^–1 of a non-resonant medium (CCl₄) using an ultrabroadband dye laser (1000 cm^–1 FWHM). The influence of the Stokes beam spatial dispersion on the width of CARS generation is demonstrated. By this method, 1060 cm^–1 wide single-pulse spectra of the OH stretching vibration of liquid water are obtained for the first time. The ratio between the resonant and non-resonant part of the third-order susceptibility in water and methanol is determined.     

Broadband coherent anti-Stokes Raman scattering spectroscopy using soliton pulse trains from a photonic crystal fiber

Pulse trains of fundamental soliton pulses with different center wavelengths and delay times from a photonic crystal fiber were generated and used as Stokes optical pulses in coherent anti-Stokes Raman scattering (CARS) spectroscopy. The pulse trains were created by shaping optical pulses with a pulse shaper and their waveforms were measured by a cross-correlation frequency-resolved optical gating method. By the use of pulse trains, the time required for obtaining broadband CARS signals was reduced to be about one third compared with our previous study without using pulse trains. With this setup, broadband CARS signals between 500 and 3100 cm⁻¹ of a single polystyrene bead sample have been measured and the most of the Raman peaks in this frequency range of samples have been observed clearly.     

Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Simultaneous measurements of global vibrational spectra and dephasing times of molecular vibrational modes by broadband time-resolved coherent anti-Stokes Raman scattering spectrography

In broadband coherent anti-Stokes Raman scattering (CARS) spectroscopy with supercontinuum (SC), the simultaneously detectable spectral coverage is limited by the spectral continuity and the simultaneity of various spectral components of SC in an enough bandwidth. By numerical simulations, the optimal experimental conditions for improving the SC are obtained. The broadband time-resolved CARS spectrography based on the SC with required temporal and spectral distributions is realised. The global molecular vibrational spectrum with well suppressed nonresonant background noise can be obtained in a single measurement. At the same time, the measurements of dephasing times of various molecular vibrational modes can be conveniently achieved from intensities of a sequence of time-resolved CARS signals. It will be more helpful to provide a complete picture of molecular vibrations, and to exhibit a potential to understand not only both the solvent dynamics and the solute-solvent interactions, but also the mechanisms of chemical reactions in the fields of biology, chemistry and material science.     

Near-quantum-limit efficiency of picosecond stimulated Raman scattering in BaWO(4) crystal

Stimulated Raman scattering of 35-ps pulses in BaWO(4) crystal was studied. The second harmonic of a Nd:YAG double-mode-locked laser system was used as a pump radiation source. The first Stokes conversion efficiency reached 38% in a single-pass setup and 85% in a double-pass setup. The second Stokes was generated with 20% (single-pass) and 50% (double-pass) conversion efficiency. Measurement of the temporal profiles of pump and first Stokes radiation with picosecond resolution was performed. The obtained conversion efficiency data were compared with the a plane-wave numerical model. BaWO(4) crystal can be considered an efficient Raman-active material for utilization in picosecond solid-state laser systems.     

Heterodyne interferometric polarization coherent anti‐Stokes Raman scattering (HIP‐CARS) spectroscopy

We demonstrate a new technique that combines polarization sensitivity of the coherent anti‐Stokes Raman scattering (CARS) response with heterodyne amplification for background‐free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP‐CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home‐built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm⁻¹ and record continuous high‐resolution Raman equivalent HIP‐CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Compact fibre-based coherent anti-Stokes Raman scattering spectroscopy and interferometric coherent anti-Stokes Raman scattering from a single femtosecond fibre-laser oscillator

We demonstrate a new approach to CARS spectroscopy by efficiently synthesizing synchronized narrow-bandwidth (less than 10 cm⁻¹) pump and Stokes pulses (frequency difference continuously tunable upto ≈3000 cm⁻¹) based on spectral compression together with second harmonic generation (in periodically-poled nonlinear crystals) of femtosecond pulses emitted by a single compact Er-fibre oscillator. For a far better signal to non-resonant background contrast, interferometric CARS (I-CARS) is demonstrated and CARS signal enhancement upto three orders of magnitude is achieved by constructive interference with an auxiliary local oscillator at anti-Stokes field, also synthesized by spectral compression of pulses emitted from the same fibre oscillator.     

Broadband nonlinear optical conversion of a high-energy diode-pumped picosecond laser

We report on a high-energy picosecond pulse generation out made of a simple and inexpensive all-solid-state diode-pumped oscillator. The system produces 200 nJ, 7-ps pulses with an average power as high as 3 W, using laser components with a total price of all opto-mechanical components of about $10,000. High-power broadband continuum generation is demonstrated in a specially selected single mode GeO₂-doped fiber.     

Effects of laser linewidth on coherent antiStokes Raman spectroscopy

Expressions for the generated antiStokes spectral density in coherent antiStokes Raman spectroscopy (CARS) are obtained, which take into account the finite linewidths of laser sources and which may be used to analyse observed spectra. Lorentzian and gaussian laser lineshapes are taken as special cases, which enable further analytic results for single and multiline CARS spectra to be derived. Emphasis is placed on scanning and broadband (multiplex) CARS techniques, and the choice of laser sources discussed from the spectral point of view. As examples of multiline spectra an analytical account of a periodic spectrum is presented and temperature measurement from Q-branch spectra is treated.     

Selective excitation and suppression of coherent anti-Stokes Raman scattering by shaping femtosecond pulses

Femtosecond coherent anti-Stokes Raman scattering (CARS) suffers from poor selectivity between neighbouring Raman levels due to the large bandwidth of the femtosecond pulses. This paper provides a new method to realize the selective excitation and suppression of femtosecond CARS by manipulating both the probe and pump (or Stokes) spectra. These theoretical results indicate that the CARS signals between neighbouring Raman levels are differentiated from their indistinguishable femtosecond CARS spectra by tailoring the probe spectrum, and then their selective excitation and suppression can be realized by supplementally manipulating the pump (or Stokes) spectrum with the $\pi $ spectral phase step.     

Ultrafast multiplex CARS investigation of vibrational characteristics in chloroform and PMMA

This paper demonstrates the femtosecond time-resolved coherent anti-Stokes Raman scattering by using folded BOXCARS geometry where an ultrashort broadband coherent white light continuum was used as Stokes pulse, and carries out the non-contact detection at long distance. The CARS signal is so easy to be detected that it can be seen even by nude eye. The C--H bonds of chloroform or PMMA were detected and the vibration modes belonging to the side chain and the main chain in PMMA were also compared. Their vibrational characteristics involved decay process and quantum beating were discussed. This modified CARS experimental technique could make up the deficiency of traditional CARS technique.     

Characterization of three-color CARS in a two-pulse broadband CARS spectrum

We demonstrate that a broadband coherent anti-Stokes Raman scattering (CARS) spectrum generated with a typical two-pulse scheme contains two distinct, significant signals: '2-color' CARS, where the pump and probe are provided by a narrowband pulse and the continuum pulse constitutes the Stokes light, and '3-color' CARS, where the pump and Stokes are provided by two different frequency components in the continuum pulse and the narrowband pulse serves as the probe. The CARS spectra from the two different mechanisms show distinct characteristics in Raman shift range, laser power dependence, and chirping dependence. We discuss the potential for a 3-color CARS signal to cover the fingerprint region with reduced photodamage of live cells. Official contribution of the National Institute of Standards and Technology; not subject to copyright in the United States.     

Quadruplex CARS micro‐spectroscopy

We demonstrate a technique for simultaneous detection of coherent anti‐Stokes Raman scattering (CARS) at four vibrational frequencies, using simple passive optical elements and without spectrally resolved detection. The technique is based on pump and Stokes femtosecond pulses selectively exciting vibrational resonances through spectral focusing. By replicating the pump and Stokes pair into four pairs, each traveling through appropriate glass elements, we simultaneously excite four different vibrational frequencies. The resulting CARS is a periodic train of intensities detected by a single photomultiplier and frequency analyzed to retrieve its Fourier coefficients. We demonstrate detection of methanol and ethanol mixtures in water and quantitative determination of their concentration owing to the improved chemical selectivity of this quadruplex CARS scheme. Copyright © 2012 John Wiley & Sons, Ltd.     

High-sensitivity coherent anti-Stokes Raman scattering microscopy with two tightly synchronized picosecond lasers

We demonstrate a significant improvement in signal-to-noise ratio in coherent anti-Stokes Raman scattering (CARS) spectroscopy/microscopy, using two highly synchronized picosecond Ti:sapphire lasers. A temporal jitter between the pulse trains from the two independent commercial lasers is reduced from a few picoseconds to ~21 fs , maintained over several hours. The tight synchronization brings the fluctuation of the CARS signal down to the shot-noise limit, leading to enhanced CARS vibrational images of living cells and polymer beads.     

Molecular dynamics in low vibrational states investigated by fs time-resolved coherent anti-Stokes Raman spectroscopy technique

The molecular dynamics process is investigated in this paper using a broadband fs time-resolved coherent anti-Stokes Raman spectroscopy (CARS) technique. By varying the timing of laser pulses, low vibrational states are started and studied on both the electronically excited B(³Π_0u⁺) state and ground X(¹Σ_0g⁺) state of iodine in the gas phase at room temperature. According to change the pump wavelength or Stokes pulse as well as the wavelength of the detection window for the CARS signal, dynamics on different potential-energy surfaces can be accessed and detected by the CARS spectroscopy. Results show that the period of the oscillation is decreased for the excited B(³Π_0u⁺) state as the wavelength of the pump pulses is increased, while it is increased for the ground X(¹Σ_0g⁺) state with the increase of the Stokes wavelength.     

Tunable light source for coherent anti-Stokes Raman scattering microspectroscopy based on the soliton self-frequency shift

We present a photonic crystal fiber (PCF)-based light source for generating tunable excitation pulses (pump and Stokes) that are applicable to coherent anti-Stokes Raman scattering (CARS) microspectroscopy. The laser employed is an unamplified Ti:sapphire femtosecond laser oscillator. The CARS pump pulse is generated by spectral compression of a laser pulse in a PCF. The Stokes pulse is generated by redshifting a laser pulse in a PCF through the soliton self-frequency shift. This setup allows for probing up to 4000 cm(-1) with a spectral resolution of approximately 25 cm(-1). We characterize the stability and robustness of CARS microspectroscopy employing this light source.