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


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.



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)


Document Type

Article - Journal

Document Version


File Type





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

Publication Date

01 Aug 2013