Localized Orbital Corrections for the Barrier Heights in Density Functional Theory

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• 作者：Michelle Lynn Hall ; Dahlia A. Goldfeld ; Arteum D. Bochevarov ; Richard A. Friesner
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2009
• 出版时间：November 10, 2009
• 年：2009
• 卷：5
• 期：11
• 页码：2996-3009
• 全文大小：230K
• 年卷期：v.5,no.11(November 10, 2009)
• ISSN：1549-9626

文摘

This work describes the extension of a previously reported empirical localized orbital correction model for density functional theory for atomization energies, ionization potentials, electron affinities, and reaction enthalpies to the correction of barrier heights. Various chemical reactions' barrier heights are corrected, including cycloadditions, cycloreversions, dipolar cycloadditions, S_N2’s, carbon and hydrogen radical reactions, sigmatropic shifts, and electrocyclizations. The B3LYP localized orbital correction version of the model reduces the number of outliers and overall mean unsigned error versus experiment or ab initio values from 3.2 to 1.3 kcal/mole for barrier heights and from 5.1 to 1.1 kcal/mole for reaction enthalpies versus B3LYP. Furthermore, the new model has essentially zero additional computational cost beyond standard DFT calculations. Although the model is heuristic and is based on multiple linear regression to experimental or ab initio data, each of the parameters is justified on chemical grounds and provides insight into the fundamental limitations of DFT, most importantly the failure of current DFT methods to accurately account for nondynamical electron correlation.