A Classical Trajectory Study of the Intramolecular Dynamics, Isomerization, and Unimolecular Dissociation of HO2
The classical dynamics and rates of isomerization and dissociation of HO2 have been studied using two potential energy surfaces (PESs) based on interpolative fittings of ab initio data: An interpolative moving least-squares (IMLS) surface [A. Li, D. Xie, R. Dawes, A. W. Jasper, J. Ma, and H. Guo, J. Chem. Phys. 133, 144306 (2010)10.1063/1.3490642] and the cubic-spline-fitted PES reported by Xu, Xie, Zhang, Lin, and Guo (XXZLG) [J. Chem. Phys. 127, 024304 (2007)10.1063/1.2753484]. Both PESs are based on similar, though not identical, internally contracted multi-reference configuration interaction with Davidson correction (icMRCI+Q) electronic structure calculations; the IMLS PES includes complete basis set (CBS) extrapolation. The coordinate range of the IMLS PES is limited to non-reactive processes. Surfaces-of-section show similar generally regular phase space structures for the IMLS and XXZLG PESs with increasing energy. The intramolecular vibrational energy redistribution (IVR) at energies above and below the threshold of isomerization is slow, especially for O-O stretch excitations, consistent with the regularity in the surfaces-of-section. The slow IVR rates lead to mode-specific effects that are prominent for isomerization (on both the IMLS and XXZLG) and modest for unimolecular dissociation to H + O2 (accessible only on the XXZLG PES). Even with statistical distributions of initial energy, slow IVR rates result in double exponential decay for isomerization, with the slower rate correlated with slow IVR rates for O-O vibrational excitation. The IVR and isomerization rates computed for the IMLS and XXZLG PESs are quantitatively, but not qualitatively, different from one another with the largest differences ascribed to the ∼2 kcal/mol difference in the isomerization barrier heights. The IMLS and XXZLG results are compared with those obtained using the global, semi-empirical double-many-body expansion DMBE-IV PES [M. R. Pastrana, L. A. M. Quintales, J. Brandão, and A. J. C. Varandas, J. Chem. Phys. 94, 8073 (1990)10.1021/j100384a019], for which the surfaces-of-section display more irregular phase space structure, much faster IVR rates, and significantly less mode-specific effects in isomerization and unimolecular dissociation. The calculated IVR results for all three PESs are reasonably well represented by an analytic, coupled three-mode energy transfer model.
J. W. Perry et al., "A Classical Trajectory Study of the Intramolecular Dynamics, Isomerization, and Unimolecular Dissociation of HO2," Journal of Chemical Physics, vol. 139, no. 8, American Institute of Physics (AIP), Oct 2013.
The definitive version is available at http://dx.doi.org/10.1063/1.4818879
Keywords and Phrases
Classical trajectories; Electronic structure calculations; Energy transfer models; Intramolecular dynamics; Intramolecular vibrational energy redistributions; Multireference configuration; Statistical distribution; Unimolecular dissociation, Calculations; Dissociation; Electronic structure; Energy transfer; Hydrogen inorganic compounds; Isomerization; Phase space methods; Quantum chemistry; Quartz; Space applications; Space platforms, Isomers
International Standard Serial Number (ISSN)
Article - Journal
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