RESUMO
Detailed analysis of the unique broadband millimeter-wave (70-360 GHz) collision-induced absorption spectra in pure CO2 and in its mixture with Ar is presented. The nature of the observed continuum absorption is examined using classical trajectory simulation along with statistical physics consideration. Bimolecular continuum is decomposed in the phase space into separate contributions from the so-called free, quasibound, and true bound molecular pairs, the proportions of which greatly vary with temperature. This partitioning is supported by consideration of the second virial coefficient and excluded volume in pure CO2, Ar, and CO2-Ar. Close similarity between collision-induced absorption in the CO2 containing gases and the water vapor continuum in the subterahertz spectral range is demonstrated. This similarity suggests that the physical principles underlying both continuum absorption phenomena have much in common and, therefore, can be used for continuum modeling.
RESUMO
The present paper aims at ab initio and laboratory evaluation of the N(2) collision-induced absorption band intensity arising from interactions between N(2) and H(2)O molecules at wavelengths of around 4 µm. Quantum chemical calculations were performed in the space of five intermolecular coordinates and varying N--N bond length using Møller-Plesset perturbation and CCSD(T) methods with extrapolation of the electronic energy to the complete basis set. This made it possible to construct the intermolecular potential energy surface and to define the surface of the N--N dipole derivative with respect to internal coordinate. The intensity of the nitrogen fundamental was then calculated as a function of temperature using classical integration. Experimental spectra were recorded with a BOMEM DA3-002 FTIR spectrometer and 2 m base-length multipass White cell. Measurements were conducted at temperatures of 326, 339, 352 and 363 K. The retrieved water-nitrogen continuum significantly deviates from the MT_CKD model because the relatively strong nitrogen absorption induced by H(2)O was not included in this model. Substantial uncertainties in the measurements of the H(2)O-N(2) continuum meant that quantification of any temperature dependence was not possible. The comparison of the integrated N(2) fundamental band intensity with our theoretical estimates shows reasonably good agreement. Theory indicates that the intensity as a function of temperature has a minimum at approximately 500 K.
RESUMO
In this article, we report on a Fourier transform infrared study of absorption bands belonging to small-sized water clusters formed in a continuous slit nozzle expansion of water vapor seeded in argon carrier gas. Clear signatures of free and H-bonded OH vibrations in water aggregates from dimer to pentamer are seen in our spectra. Following an increase in argon backing pressure, the position of the cluster absorption bands varies from those characteristics of isolated water aggregates in the gas phase to those known for clusters trapped in a static argon matrix. These variations can be interpreted in terms of sequential solvation of the water clusters by an increasing number of argon atoms attached to water clusters. Our measured spectra are in good agreement with those obtained previously either for free or Ar coated small-sized water clusters using pulsed slit-jet expansions. Our results are equally in accord with those originating from a variety of tunable laser based techniques using molecular beams or free jets or from the study of water aggregates embedded in rare gas matrices. Distinctions are reported, however, and discussed. Ab initio calculations have made it possible to speculate on the average size of an argon solvation shell around individual clusters as well as on the development of the OH stretch vibrational shifts in mixed (H(2)O)(m)Ar(n) clusters having different compositions and architectures.
