Diagrammatic representation of the third-order polarization in transient CARS

Summary A diagrammatic perturbative approach is adopted to derive the expression for the third-order polarization,P ⁽³⁾ which originates the anti-Stokes emission in a time-resolved CARS experiment. The various contributions toP ⁽³⁾ are calculated assuming that laser fields are off-resonance with respect to any electronic level of material system. The resonant part of the polarization consists of two terms, in which the roles of the pump and probe pulses at frequency ω₁ are exchanged. The global expression allows the direct calculation of the signal time profile in a transient CARS experiment once a model is assumed for the laser pulse shape.     

Nanoscale Distribution of Sulfonic Acid Groups Determines Structure and Binding of Water in Nafion Membranes

The connection between the nanoscale structure of two chemically equivalent, yet morphologically distinct Nafion fuel‐cell membranes and their macroscopic chemical properties is demonstrated. Quantification of the chemical interactions between water and Nafion reveals that extruded membranes have smaller water channels with a reduced sulfonic acid head group density compared to dispersion‐cast membranes. As a result, a disproportionally large amount of non‐bulk water molecules exists in extruded membranes, which also exhibit larger proton conductivity and larger water mobility compared to cast membranes. The differences in the physicochemical properties of the membranes, that is, the chemical constitution of the water channels and the local water structure, and the accompanying differences in macroscopic water and proton transport suggest that the chemistry of nanoscale channels is an important, yet largely overlooked parameter that influences the functionality of fuel‐cell membranes.     

Fast three‐dimensional chemical imaging by interferometric multiplex coherent anti‐Stokes Raman scattering microscopy

We report significant improvements in both signal sensitivity and imaging speed of Fourier transform spectral interferometry coherent anti‐Stokes Raman scattering (FTSI‐CARS) microscopy. With a help of an apodization function in the signal retrieval process, background due to the spectral change of nonresonant signals is eliminated. We experimentally verify that the sensitivity of the improved method is nearly shot‐noise‐limited. The current maximum detection sensitivity is ∼10 mM of aqueous sulfate ions, which correspond to ∼10⁶ oscillators in the microscopy focal volume. Operating the charge‐coupled device (CCD) in the crop mode increases the image acquisition speed by more than ten times. A vibrational hyperspectral image of a polymer sample with 100 × 100 pixel can be obtained within 3 s. With the improved sensitivity and speed, we also perform three‐dimensional volume imaging. Superior chemical selectivity is demonstrated with a mixture of two different oil droplets, which have identical vibrational peak positions but different relative peak ratios. Copyright © 2010 John Wiley & Sons, Ltd.     

CARS diagnostics of fluid adsorption and condensation in small mesopores

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy is applied to diagnostics of phase behavior of a fluid in pores of nanoporous glasses. Samples with mean pore radii of 2 and 3.5 nm were filled with compressed carbon dioxide at near‐room temperatures. CARS spectra of the 1388 cm⁻¹ Q‐branch were measured at isothermal compressing in a wide pressure range including the transition from gaseous to condensed state. The spectra show specific transformations caused by fluid adsorption and condensation in nanopores. We have carried out calculations of the spectral profiles based on the phase behavior of carbon dioxide in cylindrical glass nanopores. Phase behavior modeling was performed using thermodynamic concepts of surface adsorption and capillary condensation. A good agreement between experimental spectra and calculations was obtained. The potential of CARS technique for the diagnostics of fluid phase behavior in pores and for the characterization of nanoporous host structure is discussed. Copyright © 2011 John Wiley & Sons, Ltd.     

Herman-Wallis factor to improve thermometric accuracy of vibrational coherent anti-Stokes Raman spectra of H2

The Herman-Wallis factor is a molecular parameter that measures the influence of centrifugal force on the intensity of spectral lines. Understandably, the effect is significant for very light molecules that necessarily have large couplings between vibrational and rotational degrees of freedom. Although known, the conceptual basis of the Herman-Wallis factor are nevertheless not clearly established in the literature. Over the years, different approaches have been proposed to explain the corrections to spectral line-strengths and, recently, an experimental study has demonstrated that Q-branch Raman transitions of H₂ are highly sensitive to the theoretical model employed to determine the Herman-Wallis factor. In this paper, this fact is used to analyze the consequences on thermometry based on coherent anti-Stokes Raman scattering (CARS) designed to probe H₂ molecules in combustion studies. It is found that the different Herman-Wallis factors lead to relative thermometric disagreements from several tens up to hundreds of degrees. This analysis could explain why H₂ CARS thermometry has been considered less reliable than thermometric predictions based on CARS of more common molecules such as N₂, O₂ and others. In particular, it is remarked that unreliable expressions of Herman-Wallis factors have been used so far to interpret Q-branch H₂ CARS experiments.     

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.