Quantum dynamics study of kinetic isotope effects of OD with HBr and DBr

Literature Information

Publication Date 2019-06-07
DOI 10.1039/C9CP02706H
Impact Factor 3.676
Authors

Yuping Wang, Dunyou Wang


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Abstract

We carried out a time-dependent, full dimensional, quantum dynamics wave-packet calculation to study the isotope effects for the OD + HBr and OD + DBr reactions. Reaction cross sections and rate constants for the OD + HBr (k2) and OD + DBr (k4) reactions are compared with the ones of OH + HBr (k1) and OH + DBr (k3). The comparisons of cross sections and rate constants show that OH/OD + HBr almost has the same reactivity, as does OH/OD + DBr. Nonetheless, the OH + HBr reaction still has the largest reactivity, then OD + HBr, OH + DBr, and OD + DBr has the smallest. Furthermore, the rate constants of OD + HBr/DBr reactions have a strong negative temperature dependence below 200 K and a nearly constant temperature dependence above 200 K, agreeing with the experimental results both qualitatively and quantitatively. Our calculated quantum primary kinetic isotope effects (k1/k3 = 1.56 and k2/k4 = 1.80) and secondary kinetic isotope effects (k1/k2 = 1.11 and k3/k4 = 1.29) are temperature independent, confirming the experimental measurements, and are in very good agreement with the experimental data.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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