Analysis of the effect of changing the a0 parameter of the Becke3-LYP hybrid functional on the transition state geometries and energy barriers in a series of prototypical reactions
文献信息
Jordi Poater, Miquel Solà, Miquel Duran, Juvencio Robles
A series of eleven gas-phase chemical reactions have been examined to assess the dependence of transition state geometries and energy barriers, as well as energy differences between reactants and products, on the a0 B3LYP functional parameter. Throughout the study we have changed the a0 parameter from 0.1 to 0.9 and for the ac and ax parameters we have followed the relationships ax = 1 − a0 and ac = ax. By comparing with the QCISD transition state geometries and energy barriers, our systematic study allows us to identify the influence of the a0 parameter in the reactions studied. In general, B3LYP calculations with the original parameters underestimate energy barriers, this trend being corrected when the a0 parameter increases. Our study also shows that the fraction of Hartree–Fock exchange needed to predict accurate barrier heights differs from the optimal fraction needed to predict thermochemical properties and geometries.
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Physical Chemistry Chemical Physics

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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