Application of External-Cavity Quantum Cascade Infrared Lasers to Nanosecond Time-Resolved Infrared Spectroscopy of Condensed-Phase Samples Following Pulse Radiolysis

Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973-5000, USA.
Applied Spectroscopy (Impact Factor: 1.88). 06/2010; 64(6):563-70. DOI: 10.1366/000370210791414344
Source: PubMed


Pulse radiolysis, utilizing short pulses of high-energy electrons from accelerators, is a powerful method for rapidly generating reduced or oxidized species and other free radicals in solution. Combined with fast time-resolved spectroscopic detection (typically in the ultraviolet/visible/near-infrared), it is invaluable for monitoring the reactivity of species subjected to radiolysis on timescales ranging from picoseconds to seconds. However, it is often difficult to identify the transient intermediates definitively due to a lack of structural information in the spectral bands. Time-resolved vibrational spectroscopy offers the structural specificity necessary for mechanistic investigations but has received only limited application in pulse radiolysis experiments. For example, time-resolved infrared (TRIR) spectroscopy has only been applied to a handful of gas-phase studies, limited mainly by several technical challenges. We have exploited recent developments in commercial external-cavity quantum cascade laser (EC-QCL) technology to construct a nanosecond TRIR apparatus that has allowed, for the first time, TRIR spectra to be recorded following pulse radiolysis of condensed-phase samples. Near single-shot sensitivity of DeltaOD <1 x 10(-3) has been achieved, with a response time of <20 ns. Using two continuous-wave EC-QCLs, the current apparatus covers a probe region from 1890-2084 cm(-1), and TRIR spectra are acquired on a point-by-point basis by recording transient absorption decay traces at specific IR wavelengths and combining these to generate spectral time slices. The utility of the apparatus has been demonstrated by monitoring the formation and decay of the one-electron reduced form of the CO(2) reduction catalyst, [Re(I)(bpy)(CO)(3)(CH(3)CN)](+), in acetonitrile with nanosecond time resolution following pulse radiolysis. Characteristic red-shifting of the nu(CO) IR bands confirmed that one-electron reduction of the complex took place. The availability of TRIR detection with high sensitivity opens up a wide range of mechanistic pulse radiolysis investigations that were previously difficult or impossible to perform with transient UV/visible detection.

Download full-text


Available from: Etsuko Fujita
  • [Show abstract] [Hide abstract]
    ABSTRACT: Due to their unique properties, ionic liquids present many opportunities for basic research on the interactions of radiation with materials under conditions not previously available. At the same time, there are practical applied reasons for characterizing, understanding, and being able to predict how ionic-liquid-based devices and industrial-scale systems will perform under conditions of extreme reactivity, including radiation. This perspective discusses current issues in ionic liquid physical chemistry, provides a brief introduction to radiation chemistry, draws attention to some key findings in ionic liquid radiation chemistry, and identifies some current hot topics and new opportunities.
    No preview · Article · Nov 2010 · Journal of Physical Chemistry Letters
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: A setup is presented for ATR-IR spectroscopy based on a pulsed tunable external-cavity QCL. The electronic detection system integrates the detector signal during laser emission. Repeatable measurements of absorption spectra have been achieved.
    Preview · Conference Paper · Jan 2012
  • [Show abstract] [Hide abstract]
    ABSTRACT: Three continuous wave external cavity quantum cascade lasers (EC-QCLs) operating between 1305 and 2260 cm−1 (4.42–7.66 µm) have been tested as radiation sources for an absorption spectrometer focused on the analysis of physical and chemical phenomena in molecular plasmas. Based on the wide spectral tunability of EC-QCLs, multiple species detection has become feasible and is demonstrated in a study of low-pressure Ar/N2 microwave plasmas containing methane as a hydrocarbon precursor. Using the direct absorption technique, the evolution of the concentrations of CH4, C2H2, HCN and H2O has been monitored depending on the discharge conditions at a pressure of p = 0.5 mbar and at a frequency of f = 2.45 GHz in a planar microwave plasma reactor. The concentrations were found to be in the range of 1011–1014 molecules cm−3. In addition, based on the analysis of the line profile of selected absorption lines, the gas temperature Tg has been calculated in dependence on the discharge power. Tg increased with the power values and was in the range between 400 and 700 K. Further, in a pure He/Ar microwave plasma, the wavelength modulation spectroscopy technique has been applied for the sensitive detection of transient plasma species with absorbencies down to 10−5. The typical spectral line width of an EC-QCL under the study was found to be in the range 24 to 38 MHz depending (i) on the chopping technique used and (ii) on a single or averaged measurement approach. Further, different methods for the modulation and tuning of the laser radiation have been tested. Varying the power values of an EC-QCL between 0.1 and 154 mW for direct absorption measurements under low pressure conditions, no saturation effects in determining the concentrations of methane, acetylene and carbon monoxide could be found under the experimental conditions used, i.e. for lines with line strengths between 10−19 and 10−22 cm molecule−1.
    No preview · Article · Oct 2012 · Measurement Science and Technology
Show more