Tunneling dynamics, symmetry, and far-infrared spectrum of the rotating water trimer. II. Calculations and experiments

Abstract

With the Hamiltonian derived in the preceding paper and the ab initio potentials of T. Bürgi, S. Graf, S. Leutwyler, and W. Klopper [J. Chem. Phys. 103, 1077 (1995)] and of J. G. C. M. van Duijneveldt‐van de Rijdt and F. B. van Duijneveldt [Chem. Phys. Lett. 237, 560 (1995)], we calculate the pseudo‐rotation tunneling levels in a rotating water trimer. The internal motions are treated by a three‐dimensional discrete variable representation and the Coriolis coupling with the overall rotation is included. Also the effects of donor tunneling are included, by introducing semi‐empirical coupling matrix elements. New experimental data are presented for the c‐type band at 87.1 cm−1 in (H2O)3, which show that specific levels in the donor tunneling quartets of this band are further split into doublets. With the results of our quantitative calculations and the model of the preceding paper we can understand the mechanisms of all the splittings observed in the earlier high‐resolution spectra of (H2O)3 and (D2O)3, as well as these new splittings, in terms of pseudo‐rotation tunneling, donor tunneling and Coriolis coupling. An unambiguous assignment is given of all the bands observed and analyzed. The ab initio potential of the Van Duijneveldts yields accurate energies of the lower pseudo‐rotation levels, the potential of Bürgi et al. performs better for the higher levels. With our analysis we can deduce from the spectra that donor tunneling involves inversion of the trimer.