Development of nanosecond time-resolved infrared detection at the LEAF pulse radiolysis facility.

When coupled with transient absorption spectroscopy, pulse radiolysis, which utilizes high-energy electron pulses from an accelerator, is a powerful tool for investigating the kinetics and thermodynamics of a wide range of radiation-induced redox and electron transfer processes. The majority of these investigations detect transient species in the UV, visible, or near-IR spectral regions. Unfortunately, the often-broad and featureless absorption bands in these regions can make the definitive identification of intermediates difficult.

Mechanism of the formation of a Mn-based CO2 reduction catalyst revealed by pulse radiolysis with time-resolved infrared detection.

Using a new technique, which combines pulse radiolysis with nanosecond time-resolved infrared (TRIR) spectroscopy in the condensed phase, we have conducted a detailed kinetic and mechanistic investigation of the formation of a Mn-based CO2 reduction electrocatalyst, [Mn((t)Bu2-bpy)(CO)3]2 ((t)Bu2-bpy = 4,4'-(t)Bu2-2,2'-bipyridine), in acetonitrile. The use of TRIR allowed, for the first time, direct observation of all the intermediates involved in this process. Addition of excess [(n)Bu4N][HCO2] to an acetonitrile solution of fac-MnBr((t)Bu2-bpy)(CO)3 results in its quantitative conversion to the Mn-formate complex, fac-Mn(OCHO)((t)Bu2-bpy)(CO)3, which is a precatalyst for the electrocatalytic reduction of CO2.

Application of external-cavity quantum cascade infrared lasers to nanosecond time-resolved infrared spectroscopy of condensed-phase samples following pulse radiolysis.

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.

Dynamics of excimer formation and decay in supercritical krypton.

New infrared absorbing species are identified in the pulse radiolysis of supercritical Kr at high pressures. The species are believed to be excimers. Their formation and decay rates have been time resolved using the Laser Electron Accelerator Facility.

Mobility of electrons in supercritical krypton: role of density fluctuations.

Excess electrons were generated in supercritical krypton by means of pulsed x-ray irradiation, and the electron transport phenomena were studied. Electron signals immediately after a 30 ps pulse showed a distinctive feature characteristic of the presence of the Ramsauer-Townsend minimum in the momentum transfer cross section. The dependence of the drift velocity v(D) on field strength was found to be concave upward in the low field region and then to go through a maximum with increasing field strength, which is also typical of the presence of a minimum in the scattering cross section at an intermediate field strength.

Energetics and volume changes in electron attachment to pyrazine in supercritical xenon.

The attachment of electrons to pyrazine occurs reversibly over a wide range of pressures at and above room temperature in supercritical xenon. The rate constant for attachment increases with pressure at low pressures, passes through a maximum, and levels off at values of 1-3x10(12) m(-1) s(-1) at high pressure. The activation volumes for attachment (DeltaVa*) are quite small but show maxima near the compressibility maxima.