We report the experimental Raman spectra of the ν2 band of H2O, D2O, and HDO in the vapor phase at room temperature. A complete interpretation of the Raman intensities is carried out employing the variational rovibrational wavefunctions obtained from a Hamiltonian in Radau coordinates and an ab initio polarizability surface at 514.5 nm. We show the importance of the rotation–vibration coupling to obtain the correct line intensities. Several tables with the assignments of the individual rotational–vibrational transitions and their Raman scattering strengths are reported. From these tables, the ν2 Raman spectra can be simulated up to 2000 K for H2O, and up to 300 K for D2O and HDO.

This work was supported by the Spanish DGES, research Project PB97-1203. We are indebted to the Centro de Supercomputaci on de Galicia (CESGA), for the use of extensive computation time.

15 pages, 5 figures, 6 tables.

Peer reviewed