1Department of Chemistry, University of Cambridge, Cambridge, CB2 1EW, UK
2Department of Chemistry, University of Leicester, Leicester, LE1 7RH, UK
3Department of Physics and Astronomy, University College London, London WC1E 6BT, UK
Abstract. The absorption of solar radiation by water dimer molecules in the Earth's atmosphere can potentially act as a positive feedback effect for climate change. There seems little doubt from the results of previous laboratory and theoretical studies that significant concentrations of the water dimer should be present in the atmosphere, yet attempts to detect water dimer absorption signatures in atmospheric field studies have so far yielded inconclusive results. Here we report spectral measurements in the near-infrared in the expected region of the third overtone of the water dimer hydrogen-bonded OHb stretching vibration around 750 nm. The results were obtained using broadband cavity ringdown spectroscopy (BBCRDS), a methodology that allows absorption measurements to be made under controlled laboratory conditions but over absorption path lengths representative of atmospheric conditions. In order to account correctly and completely for overlapping absorption of monomer molecules in the same spectral region, we have also constructed a new list of spectral data (UCL08) for the water monomer in the 750–20 000 cm−1 (13 μm–500 nm) range.
Our results show that the additional lines included in the UCL08 spectral database provide a substantially improved representation of the measured water monomer absorption in the 750 nm region, particularly at wavelengths dominated by weak monomer absorption features. No absorption features which could not be attributed to the water monomer were detected in the BBCRDS experiments up to water mixing ratios more than an order of magnitude greater than those in the ambient atmosphere. The absence of detectable water dimer features leads us to conclude that, in the absence of significant errors in calculated dimer oscillator strengths or monomer/dimer equilibrium constants, the widths of water dimer features present around 750 nm must be substantially greater (~100 cm−1 HWHM) than those reported at longer wavelengths.