Development of density functionals for thermochemical kinetics

2004/05/31 by A. Daniel Boese, Jan M. L. Martin · 3 citations
Chemical Engineering · Chemistry · Physics and Astronomy · #Advanced Chemical Physics Studies #Catalysis and Oxidation Reactions #Chemical Thermodynamics and Molecular Structure #physics.chem-ph #physics.comp-ph

paper · pdf · doi:10.1063/1.1774975

published as Journal of Chemical Physics 121, 3405-3416 (2004) · J. Chem. Phys., in press (303431JCP, scheduled for August 15, 2004 issue); supplementary data available at http://theochem.weizmann.ac.il/web/papers/BMK.html

arxiv created 2004/05/31 · openalex publication_date 2004/08/10 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/08/01

Abstract

A density functional theory exchange-correlation functional for the exploration of reaction mechanisms is proposed. This functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for transition state barriers but, unlike previous attempts at such a functional, this improved accuracy does not come at the expense of equilibrium properties. This makes it a general-purpose functional whose domain of applicability has been extended to transition states, rather than a specialized functional for kinetics. The improvement in BMK rests on the inclusion of the kinetic energy density together with a large value of the exact exchange mixing coefficient. For this functional, the kinetic energy density appears to correct "back" the excess exact exchange mixing for ground-state properties, possibly simulating variable exchange.

Citations

• Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
• Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis
• Density-functional thermochemistry. III. The role of exact exchange
• The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors

Cited by

• Gold-Standard Chemical Database 137 (GSCDB137): A diverse set of accurate energy differences for assessing and developing density functionals
• A benchmark study of dioxygen complexes based on coupled cluster and density functional theory
• Anharmonic force fields and thermodynamic functions using density functional theory

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