Line-narrowing effects in the near-infrared spectrum of water and precision determination of spectroscopic parameters.

Abstract

A dual laser absorption spectrometer operating at 1.39 μm was employed to acquire high-quality absorption spectra in coincidence with the 44,1 → 44,0 line of the H2 (18)O ν1 + ν3 band, at the temperature of the triple point of water. A rather sophisticated global fitting procedure was developed and used to simultaneously fit spectra across the explored pressure range, roughly between 1 and 4Torr. Adopting the speed-dependent Galatry profile with a hypergeometric dependence of the collisional width and shift on the absorbers' velocity, we could take into account narrowing effects ascribed to collision-induced velocity changes and speed-dependence of relaxation rates. The global approach allowed us to implement and exploit some relevant physical constraints at the aim of reducing significantly statistical correlation issues among free parameters. Consequently, we demonstrated the possibility of determining pressure broadening and shifting parameters with high precision and accuracy, at the level of one part over 10(3). Furthermore, even being in the Doppler regime, it was possible to determine the effective frequency of velocity-changing collisions for self-colliding H2 (18)O molecules.