Is rotational CARS an alternative to vibrational CARS for thermometry?

Recent developments in rotational CARS thermometry and critical issues when comparing vibrational and rotational CARS thermometry are described. In particular, the development of dual broadband rotational CARS and the noise characteristics of this approach are emphasized. The difficulty with unambiguous temperature determination in vibrational CARS with unknown parameters, in particular the nonresonant background susceptibility, and the lower sensitivity of rotational CARS thermometry at flame temperatures are also discussed.     

CARS spectroscopy of radio-frequency discharge plasma in hydrogen

The population of the vibrational and rotational levels of hydrogen is studied by the narrow-and broadband CARS spectroscopy in capacitive and inductive-capacitive radio-frequency discharge plasmas. Computational codes are developed to analyze and process CARS spectra of hydrogen obtained under conditions of disturbance of thermodynamic equilibrium over internal degrees of freedom of molecules. To interpret the measurement results, a model is developed, which makes it possible to calculate the vibrational temperature in radio-frequency discharge plasmas. It is shown that the broadband CARS spectrometer in combination with the software package developed appreciably reduces the time necessary to determine the vibrational and rotational temperatures.     

Heterodyne coherent anti-Stokes Raman scattering (CARS) imaging

We have achieved rapid nonlinear vibrational imaging free of nonresonant background with heterodyne coherent anti-Stokes Raman scattering (CARS) interferometric microscopy. This technique completely separates the real and imaginary responses of nonlinear susceptibility chi(3) and yields a signal that is linear in the concentration of vibrational modes. We show that heterodyne CARS microscopy permits the detection of weak vibrational resonances that are otherwise overshadowed by the strong interference of the nonresonant background.     

High-sensitivity vibrational imaging with frequency modulation coherent anti-Stokes Raman scattering (FM CARS) microscopy

We demonstrate a new approach to coherent anti-Stokes Raman scattering (CARS) microscopy that significantly increases the detection sensitivity. CARS signals are generated by collinearly overlapped, tightly focused, and raster scanned pump and Stokes laser beams, whose difference frequency is rapidly modulated. The resulting amplitude modulation of the CARS signal is detected through a lock-in amplifier. This scheme efficiently suppresses the nonresonant background and allows for the detection of far fewer vibrational oscillators than possible through existing CARS microscopy methods.     

CARS spectra of thermally excited SF6 molecules

CARS spectra of thev ₁ mode of thermally excited SF₆ were calculated numerically. The influence of the vibrational quasicontinuum on the CARS spectra has been considered by introducing different types of the homogeneous broadening at different vibrational levels. The appearance of additional lines in the CARS spectrum due to mixing of high-lying vibrational levels by Fermi coupling was considered numerically in the frame of a simple model. A comparison of calculated and experimental spectra has been made.     

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.     

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.     

Fourier transform spectral interferometric coherent anti-Stokes Raman scattering (FTSI-CARS) spectroscopy

A novel Fourier transform spectral interferometric (FTSI) multiplex coherent anti-Stokes Raman scattering (CARS) technique is developed to extract the vibrational spectrum equivalent to the spontaneous Raman scattering. The conventional FTSI method is modified to use the internal nonresonant CARS signal as a local oscillator to perform spectral interferometry. Utilizing the causality of the coherent vibration (i.e., there should be no signal before the laser excitation), this new FTSI method recovers the entire complex vibrational spectral parameters. We demonstrate this technique with a previously reported single-pulse multiplex CARS method that uses a single phase-controlled broadband ultrafast laser pulse.     

Resonance enhanced coherent anti-stokes raman scattering and laser induced fluorescence applied to CH radicals: a comparative study

Resonance enhanced CARS and LIF have been applied to the CH radicals in a microwave excited Ar/H/CH plasma ( Pa, kW). Both techniques yield similar nonthermal rotational population distributions of CH(X) in its vibrational ground state (), which can be described by two rotational temperatures, K being in the order of the gas temperature for rotational states with , and a considerably higher for the higher rotational states. This result is in good agreement with previous resonance CARS and LIF measurements in similar plasmas. With resonance CARS additional measurements on CH in the state could be performed yielding a vibrational temperature of 2440 K, the total CH density was about m. The detection limits of both techniques are determined, in our case about CH radicals per quantum state in the detection volume, and their advantages and disadvantages are discussed. Received: 29 April 1996 / Accepted: 19 June 1996     

Comparison of dephasing times for vibrational and rotational coherent anti-Stokes Raman scattering: implications for velocimetry

Time-domain coherent anti-Stokes Raman scattering experiments have been carried out by probing vibrational and pure rotational lines of nitrogen in the Doppler broadened regime. The theoretical analysis of the transient responses outlines the role of the geometrical effects. For pure rotational CARS, it is shown that the main contribution to the dephasing of the Raman coherence results from the change in direction between the pump and anti-Stokes wave vectors whereas the difference between the modulus of these two wave vectors accounts for dephasing in vibrational CARS. Furthermore, we demonstrate that the range of operation of time-domain CARS velocimetry is extended by probing pure rotational lines. The predictions are validated by experiments which are performed both in a static gas cell and in a Mach 10 supersonic flow. Received: 30 March 2000 / Revised version: 9 June 2000 / Published online: 13 September 2000     

Vibrational frequency shifts of fluid nitrogen fundamental and hot band transitions as a function of pressure and temperature

Abstract

Coherent anti-Stokes Raman scattering (CARS) and spontaneous Raman spectroscopy have been used to obtain vibrational spectra of shock-compressed and static high-pressure fluid nitrogen, respectively. Vibrational frequencies were obtained from the CARS data using a semiclassical model for these spectra. Spontaneous Raman vibrational frequencies were determined by fitting data using a Lorentz shape line. A functional form was found for the dependence of the vibrational frequency on pressure and temperature to 40 GPa and 5000 K, respectively. The result is compared to a recent theoretical model.     

Vibrational dynamics of nitromethane mixed with IR780 dye studied by coherent anti‐stokes Raman spectroscopy

Vibrational coupling between different kinds of molecules in liquid mixture is studied by multiplex coherent anti‐Stokes Raman spectroscopy (CARS). To identify vibrational coherence, fs‐probe with high time resolution and narrowband‐probe with high spectral resolution are adopted in CARS experiments. Using liquid nitromethane (NM) mixed with organic dye IR780 perchlorate as the sample, we can clearly observe the interference between different vibrational modes. The intermolecular vibrational interaction between NM and IR780 molecules results in the vibrational coherence transfer (VCT) in the form of a change of phase correlation. Compared with symmetric bending vibration of NO₂, coherence transfer is found to be easier to take place between C―N bond of NM and vibrations of IR780, which indicates the selectivity of intermolecular vibrational interaction. The selectivity is deduced to be related to the coordination between intramolecular and collective motion of molecules. Copyright © 2016 John Wiley & Sons, Ltd.     

Combined coherent anti-Stokes Raman spectroscopy and linear Raman spectroscopy for simultaneous temperature and multiple species measurements

The simultaneous application of pure rotational coherent anti-Stokes Raman spectroscopy (CARS) and vibrational linear Raman spectroscopy (LRS) for the measurement of temperature and species concentrations in combustion systems is demonstrated. In addition to the standard rotational CARS experimental setup, only one detection system (spectrometer and intensified CCD camera) for the collection of the LRS signals was applied. The emission of the broadband dye laser used for CARS was shifted to the deep red to avoid interferences with the LRS signals located in the visible region. First experimental results from a vaporizing propane spray using an engine injection system are shown.     

Chirped-pulse adiabatic control in coherent anti-Stokes Raman scattering for imaging of biological structure and dynamics

Two novel control methods based on adiabatic passage are proposed to be implemented in coherent anti-Stokes Raman scattering (CARS) microscopy for noninvasive imaging of biological structure and dynamics. The first method provides optimal pulse-area control of the resonant vibrational transitions by using a pair of equally linear-chirped pulses. The second method, named the 'roof' method, utilizes the chirp sign variation at the central time and gives robust adiabatic excitation of the resonant vibrational mode. Both methods are robust with respect to suppression of the off-resonant transitions. The methods allow one to achieve chemical sensitivity with high resolution and can be used to obtain CARS spectra of biological molecules with efficiently suppressed background.     

All-ultraviolet time-resolved coherent anti-Stokes Raman scattering

We report all-UV coherent anti-Stokes Raman scattering (CARS) in calcite with 250-280 nm pump, Stokes, probe, and anti-Stokes light. UV CARS efficiency is approximately 7x higher than for comparable scattering in the visible, 480-540 nm. Time-resolved UV CARS reveals lengthening of the dephasing time of 1086 cm(-1) CO3(2-) internal vibrations from 4 to 7 ps with increasing vibrational excitation, consistent with a phonon depletion model.     

Ultrabroadband (>2000 cm-1) multiplex coherent anti-Stokes Raman scattering spectroscopy using a subnanosecond supercontinuum light source

We have developed ultrabroadband (>2000 cm(-1)) multiplex coherent anti-Stokes Raman scattering (CARS) spectroscopy using a subnanosecond (sub-ns) microchip laser source. A photonic crystal fiber specifically designed for sub-ns supercontinuum (SC) generation has been used for obtaining ultrabroadband Stokes radiation, which enables us to achieve simultaneous vibrational excitation in the range from 800 to 3000 cm(-1). We have successfully obtained multiplex CARS spectra for several molecular liquids. Since the CARS system using the sub-ns SC is simple and compact, it can be easily applied to ultrabroadband multiplex CARS microspectroscopy.     

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.     

Interferometric polarization coherent anti-Stokes Raman scattering (IP-CARS) microscopy

We report a novel interferometry-based polarization coherent anti-Stokes Raman scattering (IP-CARS) implementation for effectively suppressing the nonresonant background while significantly amplifying the resonant signal for vibrational imaging. By modulating the phase difference between the two interference CARS signals generated from the same sample and measuring the peak-to-peak intensity of the periodically modulated interference CARS signal, the IP-CARS technique yields a sixfold improvement in the signal-to-background ratio compared with conventional CARS while providing an approximately 20-fold amplification of the resonant CARS signal compared with conventional polarization CARS. We demonstrate this method by imaging 4.69 microm polystyrene beads and unstained human epithelial cells immersed in water.     

Tip-enhanced coherent anti-stokes Raman scattering for vibrational nanoimaging

An electric field enhanced by a metallic nanoprobe has locally induced coherent anti-Stokes Raman scattering (CARS) of adenine molecules in a nanometric DNA network structure. Owing to the third-order nonlinearity, the excitation of the CARS polarization is extremely confined to the end of the tip apex, resulting in a spatial resolution far beyond the diffraction limit of light. Our tip-enhanced CARS microscope visualized the DNA network structure at a specific vibrational frequency (approximately 1337 cm(-1)) corresponding to the ring-breathing mode of diazole of adenine molecules.     

基于光强传输方程相位成像的宽场相干反斯托克斯拉曼散射显微背景抑制

相干反斯托克斯拉曼散射(CARS)显微能够对样品的特殊化学组分进行选择性成像,无需荧光标记,在生物医学领域被广泛应用.然而,传统的CARS图像往往存在非共振背景信号.本文将基于光强传输方程的单光束相位成像技术用于CARS显微成像,来抑制CARS的非共振背景信号.该方法通过记录样品在三个相邻平面上的CARS图像,然后利用光强传输方程获取CARS光场的相位分布,最后利用共振CARS信号和非共振背景信号在相位上的差异,实现了对背景噪声的抑制.该方法无需参考光,通过三次测量可完成CARS的背景噪声抑制,具有良好的应用前景.