Water dimer vibration–rotation tunnelling levels from vibrationally averaged monomer wavefunctions

Abstract

The vibration–rotation tunnelling (VRT) spectra for the water dimer obtained by vibrationally averaging the dimer potential over accurate water monomer wavefunctions is reported. The vibrational averaging requires evaluation of the 12D dimer potential energy surface at more than 10 12 distinct geometries. The resulting vibrational spectra of the low-lying dimer states are presented and compared with both less computationally expensive methods based on fixed nuclei approximations and the recent (6+6) d adiabatic calculations of Leforestier et al. [38] (2009). The procedure gives some modest improvement in the agreement with experimental values for the vibration–rotation tunnelling (VRT) states of (H 2O) 2 and (D 2O) 2. This approach can be extended to treat dimer states involving monomer overtone excitations, which is important in obtaining water dimer spectra at infrared and visible wavelengths at atmospheric temperatures, and in characterizing the dimer contribution to the so-called water continuum absorption at these wavelengths.