A filter-based Raman spectrometer for non-invasive imaging of atmospheric water vapor.

A new instrument was designed and developed to map the spatial distribution of water vapor concentration in the atmosphere. The high spatial resolution, sensitivity, and accuracy of the instrument enable new studies of the role of turbulence on clouds and aerosols in small-scale laboratory environments. The instrument exploits Raman scattering in a multi-pass laser configuration by using a set of narrow bandpass filters and a pair of charge coupled device imaging cameras in the 90° scattering geometry. The absolute concentration of water vapor was inferred from measured ratios of H2O and N2 vibrational Raman transitions. We have measured the number densities of water molecules in the atmosphere as low as 3.5 × 1017 cm-3, with an accuracy better than 20% and as high as 7.0 × 1017 cm-3 during minutes long observations. These measurements were taken within an imaging region 6 cm in diameter, with a per-pixel resolution 2.60 mm wide by 0.16 mm tall and 1 mm deep.

Raman spectrometer for high precision temperature sensing of atmospheric gases.

We present a highly accurate Raman spectrometer capable of measuring changes in atmospheric temperature as small as 0.75 K with high spatial and temporal resolution. The spectrometer is based on a laser diode tuned to the resonant absorption line of the 85Rb isotope near 780.0 nm. A heated glass cell containing Rb atoms was used as an ultranarrowband atomic absorption notch filter with 0.3cm-1 bandwidth and optical density as high as four. This filter was placed in front of the spectrograph and blocked up to 99.99% of the elastically scattered laser light, which made it possible to resolve the pure-rotational Raman spectra of molecular atmospheric gases. The relative intensities of pure-rotational Raman transitions were then used to infer atmospheric temperature changes.

Spectroscopic and thermodynamic properties of molecular hydrogen dissolved in water at pressures up to 200 MPa.

We have measured the Raman Q-branch of hydrogen in a solution with water at a temperature of about 280 K and at pressures from 20 to 200 MPa. From a least-mean-square fitting analysis of the broad Raman Q-branch, we isolated the contributions from the four lowest individual roto-vibrational lines. The vibrational lines were narrower than the pure rotational Raman lines of hydrogen dissolved in water measured previously, but significantly larger than in the gas. The separations between these lines were found to be significantly smaller than in gaseous hydrogen and their widths were slightly increasing with pressure. The lines were narrowing with increasing rotational quantum number. The Raman frequencies of all roto-vibrational lines were approaching the values of gas phase hydrogen with increasing pressure. Additionally, from the comparison of the integrated intensity signal of Q-branch of hydrogen to the integrated Raman signal of the water bending mode, we have obtained the concentration of hydrogen in a solution with water along the 280 K isotherm. Hydrogen solubility increases slowly with pressure, and no deviation from a smooth behaviour was observed, even reaching thermodynamic conditions very close to the transition to the stable hydrogen hydrate. The analysis of the relative hydrogen concentration in solution on the basis of a simple thermodynamic model has allowed us to obtain the molar volume for the hydrogen gas/water solution. Interestingly, the volume relative to one hydrogen molecule in solution does not decrease with pressure and, at high pressure, is larger than the volume pertinent to one molecule of water. This is in favour of the theory of hydrophobic solvation, for which a larger and more stable structure of the water molecules is expected around a solute molecule.

Laser multipass system with interior cell configuration.

We ask whether it is possible to restore a multipass system alignment after a gas cell is inserted in the central region. Indeed, it is possible, and we report on a remarkably simple rearrangement of a laser multipass system, composed of two spherical mirrors and a gas cell with flat windows in the middle. For example, for a window of thickness d and refractive index of n, adjusting the mirror separation by ≈2d(1-1/n) is sufficient to preserve the laser beam alignment and tracing. This expression is in agreement with ray-tracing computations and our laboratory experiment. Insofar as our solution corrects for spherical aberrations, it may also find applications in microscopy.

Doppler width limited near-infrared Raman spectrometer.

A new ultra high resolution spontaneous Raman spectrometer with a single mode tunable laser diode as an excitation source and a 0.275 m, f/#4 spectrograph is presented. The spectrometer is expanded by an atomic vapor (Rb) absorption filter. One of the rubidium resonance lines serves as the frequency marker by absorbing selected Raman lines during the frequency scan of the excitation laser. High resolution was achieved while preserving the speed of the spectrometer. The extended spectrometer's capability was tested by differentiating overlapping Raman lines from molecular hydrogen isotopomers: H2, D2, and HD. Experiments were carried out at 300 K and pressures near 10(4) Pa. Spectral lines separated by approximately 10 Ghz (0.3 cm-1) can be resolved with this instrument with data collection times of minutes.