Молекулярная спектроскопия Молекулярная спектроскопия
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Figure 7. The spectra of water vapour in 5300 cm-1 (a), and 3700 cm-1 (b) absorption bands, obtained in the experiments of Poberovsky [73, 74] for the cases (1): H2O + N2, and (2): pure H2O (see text); the difference spectrum (2)-(1), attributed by Poberovsky to water clusters; the difference spectrum of Poberovsky, modified in this work; WD according to the model [52]. (a) Experiment [73]: T=530°K, spectral resolution FWHM=15 cm-1, L=4.83 cm (1) and 0.49 cm (2); WD simulation: line strengths and positions from [52], HWHM=28 cm-1 [54], Keq(530°K)=0.0023 atm-1 (Curtiss et al. [59] extrapolation). (b): Experiment [74]: T=503°K, spectral resolution FWHM=10 cm-1; L=0.88 cm (1) and 0.08 cm (2); WD simulation: HWHM=25 cm-1, Keq(503 K)=0.0032 atm-1.

[52] Schofield D.P., Kjaergaard H.G. Calculated OH-stretching and HOH-bending vibrational transitions in the water dimer. Phys. Chem. Chem. Phys., 2003;5:3100–5.
[54] Ptashnik I.V., Smith K.M., Shine K.P., Newnham D.A. Laboratory measurements of water vapour continuum absorption in spectral region 5000–5600 cm-1: evidence for water dimers. Q. J. R. Meteorol Soc 2004;130:2391–408.
[59] Curtiss L.A, Frurip DJ, Blander M. Studies of molecular association in H2O and D2O vapors by measurement of thermal conductivity. J. Chem. Phys. 1979;71:2703–11
[73] Poberovsky A.V. Problemy fiziki atmosfery. Sbornik Trudov Univ Leningrad 1976;13:81–7 (in Russian).
[74] Poberovsky A.V. Diss. kand. fiz-mat nauk (PhD. thesis), Leningrad University, 1976 (in Russian).



INTAS grants 00-189, 03-51-3394, гранты РФФИ 02-07-90139, 05-07-90196, 08-07-00318, 13-07-00411