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Atmospheric and Oceanic Optics

2020 year, number 2

Study of the H2O polarisability vibrational dependence by the analysis of rovibrational line shifts

V.I. Starikov
Tomsk State University of Control Systems and Radioelectronics, Tomsk, Russia
Keywords: молекула НО, поляризуемость, уширение и сдвиг спектральных линий, water molecule, polarisability, broadening and shift of spectral lines


The study of the vibrational dependence of H2O polarisability α is based on the comparison of experimental and calculated line shifts induced by argon, nitrogen, and air pressure in different H2O vibrational bands. The dependence of a on the bending vibration is expressed as a power series in the displacement Δθ of the coordinate θ of large amplitude bending motion. The coefficients of the power series were selected in the way which gives the best agreement of calculated matrix elements <ψn|α(θ)|ψn> with the values of the polarizabylity α(n) obtained in the analysis of experimental line shifts in n × ν2 H2O bands perturbed by nitrogen, oxygen, air and argon pressure. The rotational contributions in the effective polarizability of H2O is obtained and discussed. The comparison of obtained α(θ) with ab initio calculations is carried out.