Mid-infrared concentration-modulated noise-immune cavity-enhanced optical heterodyne molecular spectroscopy of a continuous supersonic expansion discharge source.

Concentration-modulated noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) is implemented for the first time on a continuous gas-flow pinhole supersonic expansion discharge source for the study of cooled molecular ions. The instrument utilizes a continuous-wave optical parametric oscillator easily tunable from 2.5 to 3.9 µm and demonstrates a noise equivalent absorption of ∼1 × 10(-9) cm(-1). The effectiveness of concentration-modulated NICE-OHMS is tested through the acquisition of transitions in the ν1 fundamental band of HN2 (+) centered near 3234 cm(-1), with a signal-to-noise of ∼40 obtained for the strongest transitions. The technique is used to characterize the cooling abilities of the supersonic expansion discharge source itself, and a Boltzmann analysis determines a rotational temperature of ∼29 K for low rotational states of HN2 (+). Further improvements are discussed that will enable concentration-modulated NICE-OHMS to reach its full potential for the detection of molecular ions formed in supersonic expansion discharges.

Broadly tunable mid-infrared noise-immune cavity-enhanced optical heterodyne molecular spectrometer.

The sensitive spectroscopic technique noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) has been successfully used in a variety of systems; however, no broadly tunable setup has been developed for the mid-infrared. To this end, we have integrated a difference frequency generation system into a NICE-OHMS setup. Initial optimization and characterization was completed with ro-vibrational spectroscopy of methane. Doppler-broadened frequency-modulated NICE-OHMS spectra were recorded at a sensitivity of 2×10(-7) cm(-1) Hz(-1/2). Sub-Doppler saturation signals (Lamb dips) were also observed using wavelength-modulated NICE-OHMS, achieving a sensitivity of ~6×10(-9) cm(-1) Hz(-1/2).

Ultra-sensitive high-precision spectroscopy of a fast molecular ion beam.

Direct spectroscopy of a fast molecular ion beam offers many advantages over competing techniques, including the generality of the approach to any molecular ion, the complete elimination of spectral confusion due to neutral molecules, and the mass identification of individual spectral lines. The major challenge is the intrinsic weakness of absorption or dispersion signals resulting from the relatively low number density of ions in the beam. Direct spectroscopy of an ion beam was pioneered by Saykally and co-workers in the late 1980s, but has not been attempted since that time. Here, we present the design and construction of an ion beam spectrometer with several improvements over the Saykally design. The ion beam and its characterization have been improved by adopting recent advances in electrostatic optics, along with a time-of-flight mass spectrometer that can be used simultaneously with optical spectroscopy. As a proof of concept, a noise-immune cavity-enhanced optical heterodyne molecular spectroscopy (NICE-OHMS) setup with a noise equivalent absorption of ~2 × 10(-11) cm(-1) Hz(-1/2) has been used to observe several transitions of the Meinel 1-0 band of N(2) (+) with linewidths of ~120 MHz. An optical frequency comb has been used for absolute frequency calibration of transition frequencies to within ~8 MHz. This work represents the first direct spectroscopy of an electronic transition in an ion beam, and also represents a major step toward the development of routine infrared spectroscopy of rotationally cooled molecular ions.

Noise immune cavity enhanced optical heterodyne velocity modulation spectroscopy.

The novel technique of cavity enhanced velocity modulation spectroscopy has recently been demonstrated as the first general absorption technique that allows for sub-Doppler spectroscopy of molecular ions while retaining ion-neutral discrimination. The previous experimental setup has been further improved with the addition of heterodyne detection in a NICE-OHMS setup. This improves the sensitivity by a factor of 50 while retaining sub-Doppler resolution and ion-neutral discrimination. Calibration was done with an optical frequency comb, and line centers for several N(2)(+) lines have been determined to within an accuracy of 300 kHz.

Refractive index measurements of solid parahydrogen.

Solid para-H2 is a promising gain medium for stimulated Raman scattering, due to its high number density and narrow Raman linewidth. In preparation for the design of a cw solid hydrogen Raman laser, we have made the first measurements, to our knowledge, of the index of refraction of a solid para-H2 crystal, in the wavelength range of 430-1100 nm. For a crystal stabilized at 4.4 K, this refractive index is measured to be n(p-H2)=1.130±0.001 at 514 nm. A slight, but significant, dependence on the final crystal-growth temperature is observed, with higher n(p-H2) at higher crystal-growth temperatures. Once a crystal is grown, it can be heated up to 10 K with no change in n(p-H2). The refractive index varies only slightly over the observed wavelength range, and no significant birefringence was observed.