Localized orbital corrections for the calculation of ionization potentials and electron affinities in density functional theory.
This paper describes the extension of a previously reported empirical localized orbital correction model to the correction of ionization potential energies (IP) and electron affinities (EA) for atoms and molecules of first and second row elements. The B3LYP localized orbital correction version of the model (B3LYP-LOC) uses 22 heuristically determined parameters that improve B3LYP DFT IP and EA energy calculations on the G2 data set of 134 molecules from a mean absolute deviation (MAD) from experiment of 0.137 to 0.039 eV. The method significantly reduces the number of outliers and overall MAD to error levels below that achieved with G2 wave function based theory; furthermore, the new model has zero additional computational cost beyond standard DFT calculations. Although the model is heuristic and is based on a multiple linear regression to experimental errors, each of the parameters is justified on physical grounds, and each provides insight into the fundamental limitations of DFT, most importantly the failure of current DFT methods to accurately account for nondynamical electron correlation.
Knoll
Eric H
EH
Department of Chemistry, Columbia University, Havemeyer Hall, MC 3110, New York, New York 10025, USA.
Friesner
Richard A
RA
D004583:Electrons; D016014:Linear Models; D008958:Models, Molecular; D015394:Molecular Structure