@article {5195,
title = {PW86-PW91 density functional calculation of vertical ionization potentials: Some implications for present-day functionals},
journal = {International Journal of Quantum Chemistry},
volume = {81},
number = {1},
year = {2001},
note = {ISI Document Delivery No.: 380EFTimes Cited: 14Cited Reference Count: 50},
month = {Jan},
pages = {34-52},
type = {Article},
abstract = {A total of 181 vertical ionization potentials (VIPs) of 41 molecules were calculated by density functional theory (DFT) employing the Perdew-Wang 1986 (PW86) exchange and Perdew-Wang 1991 (PW91) correlation functionals and using the aug-cc-pV5Z basis and experimental ground-state geometries. The overall average absolute deviation (AAD) from experiment was found to be 0.55 eV and only 0.31 eV for linear molecules but 0.86 eV for nonplanar molecules. A number of VIPs were in error by over 2 eV. In particular, DFT performed most poorly when ionization was from an orbital with highly varying density gradients (which arise from the orbital{\textquoteright}s shape or compactness or through its density being distributed over a number of atoms). Indications are that many or all present-day functionals suffer from the same failings. (C) 2001 John Wiley \& Sons, Inc.},
keywords = {ACCURATE, AROMATIC MOLECULES, CORRELATED MOLECULAR CALCULATIONS, DFT, EXCHANGE-ENERGY, functionals, GAUSSIAN-BASIS SETS, HE(II) PHOTOELECTRON-SPECTRA, ionization potential, ORGANIC-MOLECULES, PHOTO-ELECTRON SPECTRA, PW86, PW91, SPECTROSCOPY, WAVE-FUNCTIONS},
isbn = {0020-7608},
url = {://000165685400007},
author = {Shapley, W. A. and Chong, D. P.}
}