dorsal/arxiv
View SchemaDevelopment of Novel Density Functionals for Thermochemical Kinetics
| Authors | A. Daniel Boese, Jan M. L. Martin |
|---|---|
| Categories | |
| ArXiv ID | physics/0405158 |
| URL | https://arxiv.org/abs/physics/0405158 |
| DOI | 10.1063/1.1774975 |
| Journal | Journal of Chemical Physics 121, 3405-3416 (2004) |
Abstract
A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new 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.
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"abstract": "A new density functional theory (DFT) exchange-correlation functional for the\nexploration of reaction mechanisms is proposed. This new functional, denoted\nBMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for\ntransition state barriers but, unlike previous attempts at such a functional,\nthis improved accuracy does not come at the expense of equilibrium properties.\nThis makes it a general-purpose functional whose domain of applicability has\nbeen extended to transition states, rather than a specialized functional for\nkinetics. The improvement in BMK rests on the inclusion of the kinetic energy\ndensity together with a large value of the exact exchange mixing coefficient.\nFor this functional, the kinetic energy density appears to correct `back\u0027 the\nexcess exact exchange mixing for ground-state properties, possibly simulating\nvariable exchange.",
"arxiv_id": "physics/0405158",
"authors": [
"A. Daniel Boese",
"Jan M. L. Martin"
],
"categories": [
"physics.chem-ph",
"physics.comp-ph"
],
"doi": "10.1063/1.1774975",
"journal_ref": "Journal of Chemical Physics 121, 3405-3416 (2004)",
"title": "Development of Novel Density Functionals for Thermochemical Kinetics",
"url": "https://arxiv.org/abs/physics/0405158"
},
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