The hardness profile as a tool to detect spurious stationary points in the potential energy surface

In the present work, we have computed the energy and hardness profiles for a series of inter and intramolecular conformational changes at several levels of calculation. All processes studied have in common the fact that the choice of a weak methodology or a poor basis set results in the presence of...

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Bibliographic Details
Published in:The Journal of chemical physics 2004-06, Vol.120 (23), p.10914-10924
Main Authors: Torrent-Sucarrat, Miquel, Luis, Josep M, Duran, Miquel, Sola, Miquel
Format: Article
Language:English
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Summary:In the present work, we have computed the energy and hardness profiles for a series of inter and intramolecular conformational changes at several levels of calculation. All processes studied have in common the fact that the choice of a weak methodology or a poor basis set results in the presence of spurious stationary points in the energy profile. At variance with the energy profiles, the hardness profiles calculated as the difference between the vertical ionization potential and electron affinity always show the correct number of stationary points independently of the basis set and methodology used. For this reason, we have concluded that hardness profiles can be used to check the reliability of the energy profiles for those chemical systems that, because of their size, cannot be treated with high level ab initio methods.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1742793