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: 2.01). 06/2010; 64(6):563-70. DOI: 10.1366/000370210791414344
Source: PubMed

ABSTRACT 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.

  • [Show abstract] [Hide abstract]
    ABSTRACT: Ligand-to-ligand charge transfer (LLCT) states in transition metal complexes are often characterized by fractional electron transfer due to coupling of the LLCT state with many other states via the metal. We designed and characterized a compact ReI complex that displays essentially full-electron charge transfer in the LLCT excited state. The complex, [Re(DCEB)(CO)3(L)]+ (DCEB= 4,4'-dicarboxyethyl-2,2'-bipyridine), referred to as ReEBA, features two redox active ligands with strong electron accepting (DCEB) and electron donating (L is 3-dimethylaminobenzonitrile (3DMABN)) properties. The lowest energy excited state formed with a ca. 10 ps time constant and was characterized as the full-electron 3DMABNDCEB LLCT state using time-resolved infrared spectroscopy (TRIR), transient absorption spectroscopy, and DFT computations. Analysis of a range of vibrational modes helped to assign the charge transfer characteristics of the complex. The LLCT state lifetime in ReEBA shows a strong dependence on the solvent polarity and features solvent dependent frequency shifts for several vibrational reporters. The formation of a full-electron LLCT state (~92%) was enabled by tuning the redox properties of the electron accepting ligand (DCEB) and simultaneously decoupling the redox active group of the electron donating ligand (3DMABN) from the metal center. This strategy is generally applicable for designing compact transition metal complexes that have full-electron LLCT states.
    The Journal of Physical Chemistry A 06/2014; DOI:10.1021/jp5039877 · 2.78 Impact Factor
  • Source
    [Show abstract] [Hide abstract]
    ABSTRACT: In 1953, an accidental discovery by Melvin Calvin and co-workers provided the first example of a solid (the alpha-polymorph of choline chloride) showing hypersensitivity to ionizing radiation: under certain conditions, the radiolytic yield of decomposition approached 5x10(4) per 100 eV (which is four orders of magnitude greater than usual values), suggesting an uncommonly efficient radiation-induced chain reaction. Twenty years later, the still-accepted mechanism for this rare condition was suggested by Martyn Symons, but no validation for this mechanism has been supplied. Meanwhile, ionic liquids and deep eutectic mixtures that are based on choline, betainium, and other derivitized natural amino compounds are presently finding an increasing number of applications as diluents in nuclear separations, where the constituent ions are exposed to ionizing radiation that is emitted by decaying radionuclides. Thus, the systems that are compositionally similar to radiation hypersensitive solids are being considered for use in high radiation fields, where this property is particularly undesirable! In Part 5 of this series on organic cations, we revisit the phenomenon of radiation hypersensitivity and explore mechanistic aspects of radiation-induced reactions involving this class of task-specific, biocompatible, functionalized cations, both in ionic liquids and in reference crystalline compounds. We demonstrate that Symons' mechanism needs certain revisions and rethinking, and suggest its modification. Our reconsideration suggests that there cannot be conditions leading to hypersensitivity in ionic liquids.
    The Journal of Physical Chemistry B 08/2014; 118(35). DOI:10.1021/jp5049716 · 3.38 Impact Factor
  • 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.
    Laser Applications to Chemical, Security and Environmental Analysis; 01/2012

Full-text (2 Sources)

Available from
May 29, 2014