Cavity Enhanced Velocity Modulation Spectroscopy

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Over the past several decades, velocity modulation spectroscopy has been used to study dozens of molecular ions of astronomical importance. This technique has been so productive because it provides the advantage of ion-neutral discrimination, which is critically important when interfering neutral molecules are many orders of magnitude more abundant, and when combined with heterodyne techniques, its sensitivity can approach the shot noise limit. Traditionally, velocity modulation experiments have utilized unidirectional multipass White cells to achieve up to about 8 passes through a positive column discharge cell. But by positioning the cell within an optical cavity, it is possible to obtain an effective path length orders of magnitude longer than was previously possible.
We have demonstrated this novel technique using a Ti:Sapp laser in the near-IR to observe rovibronic transitions of N2+. By demodulating at twice the modulation frequency, 2nd derivative-like lineshapes are observed for ions that are velocity-modulated, while Gaussian lineshapes are observed for excited neutral that are concentration-modulated. The signals for N2+ and N2+* have been observed to be 78° out of phase with one another, so ion-neutral discrimination is retained. And due to the laser power enhancement and geometry of the optical cavity, Doppler-free saturation spectroscopy is now possible. Observed Lamb dips have widths of 50 MHz, and when combined with calibration by an optical frequency comb, this allows for determination of line centers to within 1 MHz.
In our original demonstration of this technique, our sensitivity was limited by noise in the laser-cavity lock. Since then, we have integrated Noise Immune Cavity Enhanced Optical Heterodyne Molecular Spectroscopy (NICE-OHMS) by adding sidebands to the laser at an exact multiple of the cavity free spectral range, and demodulating at the sideband frequency before sending the signal to a lock-in amplifier for demodulating at twice the plasma frequency. This has greatly reduced the noise and increased the sensitivity of cavity enhanced velocity modulation spectroscopy.

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