The Development of a High-Power, Pulsed Mid-Infrared Laser for a Two-Photon LIF Detection of Tropospheric OH

Abstract:

The hydroxyl radical is universally recognized as the dominant oxidizing species in the earth’s atmosphere. OH initiates the chemical transformation and degradation of greenhouse gases, pollutants, and volatile organic compounds and plays a critical role in both urban ozone pollution and aerosol formation. Because of its high reactivity, OH radicals have an atmospheric lifetime of less than a second and only reach mixing ratios of parts per trillion (ppt) in the free troposphere. The combination of these two factors makes in-situ observations of OH challenging. Laser-Induced Fluorescence (LIF) is a highly sensitive technique that has been successfully applied to measurements of stratospheric OH. The LIF technique has also been adapted to instrumentation for OH observations in the troposphere. However, results for tropospheric OH have been inconclusive due to poorly understood interferences, and large discrepancies exist between modeled and measured OH concentrations. A Two-Photon LIF (TP-LIF) technique has been proposed as a means of enhancing sensitivity by shifting to lower-energy pumping frequencies, which also minimizes laser-induced interference pathways. In this detection scheme, OH is pumped into an excited vibrational state and subsequently pumped into an excited electronic state. A major limitation in the sensitivity of the TP-LIF detection scheme has been the lack of a mid-infrared (mid-IR) light source with enough power to adequately pump the vibrational transition. We have developed a high-power, pulsed laser system at 2.97 μm using an optical parametric generator (OPG). The OPG system delivers narrow-linewidth, tunable radiation with high peak-power to substantially populate the vibrational excitation. The development of the OPG laser system effectively addresses the major challenge in the TP-LIF detection of OH.