Possibilities of the observation of the discrete spectrum of the water dimer at equilibrium in millimeter-wave band

• Published in: Journal of quantitative spectroscopy & radiative transfer 2009-05, Vol.110 (8), p.427-434
• Main Authors: Krupnov, A.F., Tretyakov, M.Yu, Leforestier, C.
• Format: Article
• Language: English
• Subjects: Ab-initio calculations; Equilibrium conditions; Line- and band-widths; Millimeter-waves; Spectral features; Water dimer
• ISSN: 0022-4073; 1879-1352
• DOI: 10.1016/j.jqsrt.2009.01.022

Attempts of experimental observations of the water dimer spectrum at equilibrium conditions have lasted for more than 40 years since the dimeric hypothesis for extra absorption, but have not yielded any positive confirmed result. In the present paper a new approach is considered: using a high-resolution millimeter-wave spectrum of the water dimer at equilibrium, calculated by a rigorous fully quantum method, we show the potential existence of discernible spectral series of discrete features of the water dimer, which correspond to J+1← J, K lines of E 1 symmetry, already observed in cold molecular beam experiments and having, therefore, well-defined positions. The intensity of spectral series and contrast to the remaining continuum-like spectrum of the dimer are calculated and compared with the monomer absorption. The suitability of two types of microwave spectrometers for observing these series is considered. The collisional line-width of millimeter lines of the dimer at equilibrium is estimated and the width of IR dimer bands is discussed. It is pointed out that the large width of IR dimer bands may pose difficulties for their reliable observation and conclusive separation from the rest of absorption in water vapor. This situation contrasts with the suggested approach of dimer detection in millimeter-waves.