Abstract
Using a recent, full-dimensional, ab initio potential energy surface [Y. Wang, X. Huang, B. C. Shepler, B. J. Braams, and J. M. Bowman, J. Chem. Phys. 134, 094509 (2011)] together with rigorous diffusion Monte Carlo calculations of the zero-point energy of the water trimer, we report dissociation energies, D(0), to form one monomer plus the water dimer and three monomers. The calculations make use of essentially exact zero-point energies for the water trimer, dimer, and monomer, and benchmark values of the electronic dissociation energies, D(e), of the water trimer [J. A. Anderson, K. Crager, L. Fedoroff, and G. S. Tschumper, J. Chem. Phys. 121, 11023 (2004)]. The D(0) results are 3855 and 2726 cm(-1) for the 3H(2)O and H(2)O + (H(2)O)(2) dissociation channels, respectively, and 4206 and 2947 cm(-1) for 3D(2)O and D(2)O + (D(2)O)(2) dissociation channels, respectively. The results have estimated uncertainties of 20 and 30 cm(-1) for the monomer plus dimer and three monomer of dissociation channels, respectively.
Highlights
For a general water cluster consisting of N monomers, there are N-1 dissociation channels ranging from dissociation of a single monomer to complete “monomerization” of the cluster
The 3-body fitted potential is much more computer intensive to evaluate than the 2-body potential and so two 3-body fits were done
One is of maximum total polynomial order 5 and the other of order 6. These 12-3-body potentials combine to make the general PES for arbitrary number of monomers; they are denoted WHBB/3b5 or WHBB/3b6, depending on whether the more efficient 5thor 6th-order 3-body fit is used. (Higher-body, long-range interactions have been incorporated into this PES.10) Both versions of this PES have been shown to accurately reproduce stationary points and electronic dissociations energies, De, for clusters as large as 22 monomers, which are the largest clusters for which reliable benchmarks ab initio results are available
Summary
The dissociation energy of water clusters is an important topic that has received considerable attention theoretically.1–10 For a general water cluster consisting of N monomers, there are N-1 dissociation channels ranging from dissociation of a single monomer to complete “monomerization” of the cluster. (Received 19 August 2011; accepted 19 September 2011; published online 3 October 2011)
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