From Ab Initio Potential Energy Surfaces to State-resolved Reactivities: X + H₂O ↔ HX + OH [X = F, Cl, and O(³P)] Reactions


We survey the recent advances in theoretical understanding of quantum state resolved dynamics, using the title reactions as examples. It is shown that the progress was made possible by major developments in two areas. First, an accurate analytical representation of many high-level ab initio points over a large configuration space can now be made with high fidelity and the necessary permutation symmetry. the resulting full-dimensional global potential energy surfaces enable dynamical calculations using either quasi-classical trajectory or more importantly quantum mechanical methods. the second advance is the development of accurate and efficient quantum dynamical methods, which are necessary for providing a reliable treatment of quantum effects in reaction dynamics such as tunneling, resonances, and zero-point energy. the powerful combination of the two advances has allowed us to achieve a quantitatively accurate characterization of the reaction dynamics, which unveiled rich dynamical features such as steric steering, strong mode specificity, and bond selectivity. the dependence of reactivity on reactant modes can be rationalized by the recently proposed sudden vector projection model, which attributes the mode specificity and bond selectivity to the coupling of reactant modes with the reaction coordinate at the relevant transition state. the deeper insights provided by these theoretical studies have advanced our understanding of reaction dynamics to a new level.



Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Calculations; Dynamics; Molecular physics; Potential energy; Potential energy surfaces; Quantum chemistry; Quantum electronics, Ab initio potential energy surface; Dynamical calculations; Global potential energy surfaces; Permutation symmetry; Quantum dynamical methods; Quantum mechanical method; Quasiclassical trajectories; Reaction coordinates, Quantum theory

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version


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© 2015 American Chemical Society (ACS), All rights reserved.

Publication Date

01 May 2015