A new many-body potential energy surface for HCl clusters and its application to anharmonic spectroscopy and vibration-vibration energy transfer in the HCl trimer.
The hydrogen bond has been studied by chemists for nearly a century. Interest in this ubiquitous bond has led to several prototypical systems emerging to studying its behavior. Hydrogen chloride clusters stand as one such example. We present here a new many-body potential energy surface for (HCl)n constructed from one-, two-, and three-body interactions. The surface is constructed from previous highly accurate, semiempirical monomer and dimer surfaces, and a new high-level ab initio permutationally invariant full-dimensional three-body potential. The new three-body potential is based on fitting roughly 52,000 three-body energies computed using coupled cluster with single, doubles, perturbative triples, and explicit correlation and the augmented correlation consistent double-ζ basis set. The first application, described here, is to the ring HCl trimer, for which the many-body representation is exact. The new potential describes all known stationary points of the trimer as well its dissociation to either three monomers or a monomer and a dimer. The anharmonic vibrational energies are computed for the three H-Cl stretches, using explicit three-mode coupling calculations and local-monomer calculations with Hückel-type coupling. Both methods produce frequencies within 5 cm(-1) of experiment. A wavepacket calculation based on the Hückel model and full-dimensional classical calculation are performed to study the monomer H-Cl stretch vibration-vibration transfer process in the ring HCl trimer. Somewhat surprisingly, the results of the quantum and classical calculations are virtually identical, both exhibiting coherent beating of the excitation between the three monomers. Finally, this representation of the potential is used to study properties of larger clusters, namely to compute optimized geometries of the tetramer, pentamer, and hexamer and to perform explicit four-mode coupling calculations of the tetramer's anharmonic stretch frequencies. The optimized geometries are found to be in agreement with those of previous ab initio studies and the tetramer's anharmonic frequencies are computed within 11 cm(-1) of experiment.
Cherry L. Emerson Center for Scientific Computation and Department of Chemistry, Emory University , Atlanta, Georgia 30322, United States.
John S
JS
Mancini
Joel M
JM
Bowman