Development of Novel Density Functionals for Thermochemical Kinetics

Development of Novel Density Functionals for Thermochemical Kinetics

in press (303431JCP); Received April 9, 2004; Accepted May 28, 2004 | A. Daniel Boese* and Jan M. L. Martin†
The paper introduces a new density functional theory (DFT) exchange-correlation functional, denoted BMK (Boese-Martin for Kinetics), designed to improve the accuracy of transition state barriers while maintaining good performance for equilibrium properties. The functional includes the kinetic energy density and a large value of the exact exchange mixing coefficient, which helps correct for excessive exact exchange in ground-state properties. The BMK functional is parametrized using a large and diverse training set, achieving performance comparable to specialized functionals for transition states and outperforming traditional general-purpose functionals in most energetic properties. The BMK functional is particularly effective for transition metal complexes and is considered a reliable general-purpose functional with expanded applicability to transition states. The paper also discusses the limitations of other functionals and highlights the advantages of BMK in computational studies of reaction mechanisms.The paper introduces a new density functional theory (DFT) exchange-correlation functional, denoted BMK (Boese-Martin for Kinetics), designed to improve the accuracy of transition state barriers while maintaining good performance for equilibrium properties. The functional includes the kinetic energy density and a large value of the exact exchange mixing coefficient, which helps correct for excessive exact exchange in ground-state properties. The BMK functional is parametrized using a large and diverse training set, achieving performance comparable to specialized functionals for transition states and outperforming traditional general-purpose functionals in most energetic properties. The BMK functional is particularly effective for transition metal complexes and is considered a reliable general-purpose functional with expanded applicability to transition states. The paper also discusses the limitations of other functionals and highlights the advantages of BMK in computational studies of reaction mechanisms.
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