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J Phys Chem A. 2005 Sep 22;109(37):8348-55.

Calculation of ionization potentials of small molecules: a comparative study of different methods.

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Laboratoire de Physico-Chimie Moléculaire-UMR 5624-FR 2606, CNRS--Université de Pau et des Pays de l'Adour, Av. de l'Université, BP 1155, 64013 Pau Cedex, France.


With the help of various theoretical methods, ionization potentials (IPs) have been computed for a panel of small molecules containing atoms of group 14, 15, or 16 and representing different singly, doubly, or triply bonded systems with or without an interacting heteroatom lone pair. Comparison of experimental IP values to theoretical results indicates that (i) the standard outer valence green function (OVGF), density functional theory (DFT), and DeltaSCF methods lead to rather accurate values, (ii) the CASPT2 method systematically underestimates IPs, (iii) the method of deducing IPs from a shift of some standard DFT eigenvalue spectrum is a straightforward approach leading to rather accurate IPs, (iv) the eigenvalue spectrum obtained with the so-called statistical average of different orbital model potential (SAOP) exchange-correlation model potential is an efficient approach leading directly to quite accurate IPs, and (v) a good prediction of the IP spectrum can be obtained from the shifted excitation spectra of the system calculated by the time-dependent DFT (TD-DFT) method. It is also shown that the TD-DFT calculations of the ionized species bring a significant improvement over the calculations of the neutral molecules, indicating that a great part of the electronic relaxation is already taken into account (in a similar way for all ionizations). Finally, in the case of TD-DFT calculations of neutral molecules, the statistical average of different orbital model potential (SAOP) functional does not lead to significantly better results than the B3LYP functional.

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