High band-width mid-infrared frequency-modulated Faraday rotation spectrometer for time resolved measurement of the OH radical.

We present a novel mid-infrared frequency-modulated Faraday rotation spectrometer (FM-FRS) for highly sensitive and high bandwidth detection of OH radicals in a photolysis reactor. High frequency modulation (up to 150 MHz) of the probe laser using an electro-optical modulator (EOM) was used to produce a modulation sideband on the laser output. An axial magnetic field was applied to the multi-pass Herriott cell, causing the linearly polarized light to undergo Faraday rotation. OH radicals were generated in the cell by photolyzing a mixture of ozone (O) and water (HO) with a UV laser pulse. The detection limit of OH reaches 6.8 × 10 molecule/cm (1σ, 0.2 ms) after 3 and falling to 8.0 × 10 molecule/cm after 100 event integrations. Relying on HITRAN absorption cross section and line shape data, this corresponds to minimum detectable fractional absorption (A) of 1.9 × 10 and 2.2 × 10, respectively. A higher signal-to-noise ratio and better long-term stability was achieved than with conventional FMS because the approach was immune to interference from diamagnetic species and residual amplitude modulation noise. To our knowledge, this work reports the first detection of OH in a photolysis reactor by FM-FRS in the mid-infrared region, a technique that will provide a new and alternative spectroscopic approach for the kinetic study of OH and other intermediate radicals.