Infrared water vapor continuum absorption at atmospheric temperatures

Abstract

We have used a continuous-wave carbon dioxide laser in a single-mode realization of cavity ring-down spectroscopy to measure absorption coefficients of water vapor at 944 cm(-1) for several temperatures in the range 270-315 K. The conventional description of water vapor infrared absorption is applied, in which the absorption is modeled in two parts consisting of local line absorption and the remaining residual absorption, which has become known as the water vapor continuum. This water vapor continuum consists of distinct water-water, water-nitrogen, and water-oxygen continua. The water-water continuum absorption coefficient is found to have a magnitude of C(s)(296 K) = (1.82+/-0.02) x 10(-22) cm(2) molecule(-1) atm(-1), and the water-nitrogen coefficient has a magnitude of C(n)(296 K) = (7.3 +/- 0.4) x 10(-25) cm(2) molecule(-1) atm(-1). The temperature dependences of both the water-water and the water-nitrogen continua are shown to be well represented by a model describing the expected behavior of weakly bound binary complexes. Using this model, our data yield dissociation energies of D(e) = (-15.9 +/- 0.3) kJ/mole for the water dimer and D(e) = (-3.2 +/- 1.7) kJ/mole for the water-nitrogen complex. These values are in excellent agreement with recent theoretical predictions of D(e) = -15.7 kJ/mole (water dimer) and D(e) = -2.9 kJ/mole (water-nitrogen complex), as well as the experimentally determined value of D(e) = (-15.3 +/- 2.1) kJ/mole for the water dimer obtained by investigators employing a thermal conductivity technique. Although there is reasonably good agreement with the magnitude of the continuum absorption coefficients, the agreement on temperature dependence is less satisfactory. While our results are suggestive of the role played by water dimers and water complexes in producing the infrared continuum, the uncertain spectroscopy of the water dimer in this spectral region prevents us from making a firm conclusion. In the meantime, empirical models of water vapor continuum absorption, essential for atmospheric radiative transfer calculations, should be refined to give better agreement with our low-uncertainty continuum absorption data.