Communication: Quasiclassical trajectory calculations of correlated product-state distributions for the dissociation of (H2O)2 and (D2O)2

G. Czakó, Yimin Wang, Joel M. Bowman

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

Stimulated by recent experiments B. E. Rocher-Casterline, L. C. Chng, A. K. Mollner, and H. Reisler, J. Chem. Phys. 134, 211101 (2011), we report quasiclassical trajectory calculations of the dissociation dynamics of the water dimer, (H2O)2 (and also (D2O)2) using a full-dimensional ab initio potential energy surface. The dissociation is initiated by exciting the H-bonded OH(OD)-stretch, as done experimentally for (H2O)2. Normal mode analysis of the fragment pairs is done and the correlated vibrational populations are obtained by (a) standard histogram binning (HB), (b) harmonic normal-mode energy-based Gaussian binning (GB), and (c) a modified version of (b) using accurate vibrational energies obtained in the Cartesian space. We show that HB allows opening quantum mechanically closed states, whereas GB, especially via (c), gives physically correct results. Dissociation of both (H2O)2 and (D 2O)2 mainly produces either fragment in the bending excited (010) state. The H2O(J) and D2O(J) rotational distributions are similar, peaking at J 3-5. The computations do not show significant difference between the ro-vibrational distributions of the donor and acceptor fragments. Diffusion Monte Carlo computations are performed for (D2O)2 providing an accurate zero-point energy of 7247 cm-1, and thus, a benchmark D0 of 1244 5 cm-1.

Original languageEnglish
Article number151102
JournalThe Journal of Chemical Physics
Volume135
Issue number15
DOIs
Publication statusPublished - Oct 21 2011

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communication
Trajectories
fragments
trajectories
dissociation
histograms
Communication
products
Potential energy surfaces
zero point energy
Excited states
Dimers
potential energy
dimers
harmonics
energy
Water
water
excitation
Experiments

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Communication : Quasiclassical trajectory calculations of correlated product-state distributions for the dissociation of (H2O)2 and (D2O)2. / Czakó, G.; Wang, Yimin; Bowman, Joel M.

In: The Journal of Chemical Physics, Vol. 135, No. 15, 151102, 21.10.2011.

Research output: Contribution to journalArticle

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