PNNL

Abstract

We report the first optimum geometries and harmonic vibrational frequencies for the ring pentamer and several water hexamer (prism, cage, cyclic and two book) at the CCSD(T)/aug-cc-pVDZ level of theory. All five hexamer isomer minima previously reported by MP2 are also minima on the CCSD(T) potential energy surface (PES). In addition, all CCSD(T) minimum energy structures for the n=2-6 cluster isomers are quite close to the ones previously obtained by MP2 on the respective PESs, as confirmed by a modified Procrustes analysis that quantifies the difference between any two cluster geometries. The CCSD(T) results confirm the cooperative effect of the homodromic ring networks (systematic contraction of the nearest-neighbor (nn) intermolecular separations with cluster size) previously reported by MP2, albeit with O-O distances shorter by ~0.02 Å, indicating that MP2 overcorrects this effect. The harmonic frequencies at the minimum geometries were obtained by the double differentiation of the CCSD(T) energy using an efficient scheme based on internal coordinates that reduces the number of required single point energy evaluations by ~15% when compared to the corresponding double differentiation using Cartesian coordinates. Negligible differences between MP2 and CCSD(T) are found for the librational modes, while uniform increases of ~15 and ~25 cm-1 are observed for the bending and “free” OH harmonic frequencies. The largest differences between MP2 and CCSD(T) are observed for the harmonic hydrogen bonded frequencies. The CCSD(T) red shifts from the monomer frequencies (??) are smaller than the MP2 ones, due to the fact that the former produces shorter elongations (?R) of the respective hydrogen bonded OH lengths from the monomer value with respect to the latter. Both the MP2 and CCSD(T) results for the hydrogen bonded frequencies were found to closely follow the relation - ?? = s · ?R, with a rate of s = 20.3 cm-1 / 0.001 Å. The CCSD(T) harmonic frequencies, when corrected using the MP2 anharmonicities obtained from second order vibrational perturbation theory (VPT2), produce anharmonicCCSD(T) estimates that are within