Kinetic and Dynamic Studies of the Cl(²Pu) + H ₂O(X¹A₁) → HCl(X¹Σ⁺) + OH(X²Π) Reaction on an Ab Initio Based Full-dimensional Global Potential Energy Surface of the Ground Electronic State of ClH₂O

Abstract

Extensive high-level ab initio calculations were performed on the ground electronic state of ClH2O. the barrier region for the title reaction was found to have significant multi-reference character, thus favoring the multi-reference configuration interaction (MRCI) method over single-reference methods such as coupled-cluster. a full-dimensional global potential energy surface was developed by fitting about 25 000 MRCI points using the permutation invariant polynomial method. the reaction path features a "late" barrier flanked by deep pre- and post-barrier wells. Calculated rate constants for the forward reaction are in reasonable agreement with experiment, suggesting a good representation of the forward barrier. the dynamics of the forward reaction was also investigated using a quasi-classical trajectory method at energies just above the barrier. While the OH bond is found to be a spectator, the HCl product has significant rotational excitation. the reaction proceeds via both direct rebound and stripping mechanisms, leading to backward and sideways scattering.

Department(s)

Chemistry

Keywords and Phrases

Global potential energy surfaces; Ground electronic state; High-level ab initio calculations; Invariant polynomials; Multireference configuration; Quasi-classical trajectory method; Rotational excitation; Stripping mechanisms; Calculations; Electronic states; Quantum chemistry; Rate constants; Potential energy surfaces

International Standard Serial Number (ISSN)

0021-9606

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2013, American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Aug 2013

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