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Predicting Reaction Outcomes02:24

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Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...
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Local hybrid functionals: an assessment for thermochemical kinetics.

Martin Kaupp1, Hilke Bahmann, Alexei V Arbuznikov

  • 1Institut für Anorganische Chemie, Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany. kaupp@mail.uni-wuerzburg.de

The Journal of Chemical Physics
|November 27, 2007
PubMed
Summary

New local hybrid functionals in density functional theory offer improved accuracy for molecular energies and reaction barriers. A simple Lh-SVWN functional shows superior performance, especially for larger molecules, outperforming existing methods.

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Multiscale Sampling of a Heterogeneous Water/Metal Catalyst Interface using Density Functional Theory and Force-Field Molecular Dynamics

Published on: April 12, 2019

Area of Science:

  • Computational chemistry
  • Quantum chemistry
  • Materials science

Background:

  • Density functional theory (DFT) is crucial for predicting molecular properties.
  • Standard DFT functionals face limitations in accuracy for thermochemistry and kinetics.
  • Local hybrid functionals offer a promising avenue for enhanced predictive power.

Purpose of the Study:

  • To evaluate the performance of local hybrid functionals with varying local mixing functions (LMFs).
  • To assess their accuracy for heats of formation and reaction barriers.
  • To identify the most effective local hybrid functional for chemical applications.

Main Methods:

  • Validation of local hybrid functionals against the G3/99, HTBH38, and NHTBH38 datasets.
  • Systematic analysis of local mixing functions (LMFs) governing position-dependent exact-exchange admixture.
  • Graphical analysis of LMFs in real space to understand functional performance.

Main Results:

  • A simple local hybrid Lh-SVWN functional demonstrated superior accuracy for thermochemistry and kinetics.
  • Lh-SVWN significantly reduced mean absolute errors compared to global hybrid functionals.
  • This functional avoided the deterioration observed with standard functionals for larger molecules.

Conclusions:

  • Local hybrid functionals, particularly Lh-SVWN, represent a significant advancement in DFT accuracy.
  • The chosen one-parameter LMF in Lh-SVWN is effective for both thermochemistry and kinetics.
  • Further development of local hybrids based on generalized gradient approximation exchange proved less fruitful.