Sensitive CH4 detection applying quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy.

We report on sensitive detection of atmospheric methane employing quantum cascade laser based optical feedback cavity-enhanced absorption spectroscopy (OF-CEAS). An instrument has been built utilizing a continuous-wave distributed feedback quantum cascade laser (cw-QCL) with a V-shaped cavity, a common arrangement that reduces feedback to the laser from non-resonant reflections. The spectrometer has a noise equivalent absorption coefficient of 3.6 × 10-9 cm-1 Hz-1/2 for a spectral scan of CH4 at 7.39 µm. From an Allan-Werle analysis a detection limit of 39 parts per trillion of CH4 at atmospheric pressure within 50 s acquisition time was found.

Rapid passage signals from a vibrationally excited target molecule: a pump and probe experiment with continuous wave quantum cascade lasers.

Two 5 µm continuous wave quantum cascade lasers are used to perform a counterpropagating pump and probe experiment on a low pressure sample of nitric oxide. The strong pump field excites a fundamental rovibrational transition and the weaker probe field is tuned to the corresponding rotationally resolved hot band transition. When both light fields are in resonance, rapid passage is observed in the hot band absorption lineshape arising from a minimally damped and velocity-selected sample of molecules in the v=1 state. The measured rapid passage signals are well described by a two-level model based on the optical Bloch equations.

Rapid passage signals induced by chirped quantum cascade laser radiation: K state dependent-delay effects in the nu2 band of NH3.

In this Letter, a 10 microm quantum cascade laser operating in the intrapulse mode is used observe rapid passage (RP) effects within a 40 cm single-pass gas cell containing low pressures of NH(3). The laser tuning range allows the rotational states J=2 with K=0, 1, and 2 to be probed. We show that the RP structures change as a function of optical density and that the magnitude of the delay in the switch from absorption to emission as a function of increased gas pressure is dependent upon the initial value of K. These measurements are qualitatively well modeled using the Maxwell-Bloch equations.

Characterization of an external cavity diode laser based ring cavity NICE-OHMS system.

The performance of an external cavity diode laser based noise immune cavity enhanced optical heterodyne molecular spectrometer is presented. To reduce the noise on the signal a ring cavity and a circuit to remove residual amplitude modulation on the pre-cavity laser radiation was implemented. We demonstrate a sensitivity of 4 x 10(-11) cm(-1) Hz(-1/2) using a cavity with a finesse of 2600 on a Doppler-broadened transition of CH(4) at 6610.063 cm(-1).

Production mechanisms of NH and NH2 radicals in N2-H2 plasmas.

We measured the densities of NH and NH(2) radicals by cavity ring-down spectroscopy in N(2)-H(2) plasmas expanding from a remote thermal plasma source and in N(2) plasmas to which H(2) was added in the background. The NH radical was observed via transitions in the (0,0), (1,1), and (2,2) vibrational bands of the A(3)Pi <-- X(3)Sigma- electronic transition and the NH(2) radical via transitions in the (0,9,0) <-- (0,0,0) band of the A(2)A(1) <-- X(2)B(1) electronic transition. The measurements revealed typical densities of 5 x 10(18) m(-3) for the NH radical in both plasmas and up to 7 x 10(18) m(-3) for the NH(2) radical when N(2) and H(2) are both fed through the plasma source. In N(2) plasma with H(2) injected in the background, no NH(2) was detected, indicating that the density is below our detection limit of 3 x 1016 m-3. The error in the measured densities is estimated to be around 20%. From the trends of the NH(x) radicals as a function of the relative H(2) flow to the total N(2) and H(2) flow at several positions in the expanding plasma beam, the key reactions for the formation of NH and NH(2) have been determined. The NH radicals are mainly produced via the reaction of N atoms emitted by the plasma source with H(2) molecules with a minor contribution from the reaction of N+ with H(2). The NH(2) radicals are formed by reactions of NH(3) molecules, produced at the walls of the plasma reactor, and H atoms emitted by the plasma source. The NH radicals can also be produced by H abstraction of NH(2) radicals. The flux densities of the NH(x) radicals with respect to the atomic radicals are appreciable in the first part of the expansion. Further downstream the NH(x) radicals are dissociated, and their densities become smaller than those of the atomic radicals. It is concluded that the NH(x) radicals play an important role as precursors for the N and H atoms, which are key to the surface production of N(2), H(2), and NH(3) molecules.