Terahertz laser spectroscopy of the water dimer intermolecular vibrations. II. (H2O)2

Terahertz VRT laser spectra of four (H2O)2 intermolecular vibrations consisting of 362 transitions have been measured between 87 and 108 cm−1 with ca. 2 MHz precision. The results differ both qualitatively and quantitatively from the predictions of dimer potentials tested. The spectra also reveal an ordering of the intermolecular vibrations which differs dramatically from that predicted by normal mode analysis. Strong coupling is indicated between the low barrier tunneling motions and the intermolecular vibrations as well as among different vibrations. In particular the 102.1 cm−1 (H2O)2 vibration assigned as the acceptor wag (ν8) exhibits two types of perturbations. In one of these a component of Ka=1 coupling with a tunneling component of Ka=0 in the 108 cm−1 acceptor twist (ν11) vibration. There is also an indication that the 103.1 cm−1 (H2O)2 band assigned as the donor in-plane bend (ν6) is coupled to the acceptor wag resulting in a lower of the in-plane bend frequency and a higher acceptor wag frequency. Detailed analysis of the VRT levels confirms the extreme nonrigidity of this complex, indicating that the use of approximate models with reduced dimensionality to calculate its properties are likely to fail.