Title 



Chemical and ionization potentials : relation via the Pauli potential and NOF theory
 
Author 



 
Abstract 



HartreeFock (HF) theory makes the prediction that for neutral atoms the chemical potential (l) is equal to minus the ionization potential (I). This has led us to inquire whether this intimate relation is sensitive to electron correlation. We present here therefore some discussion of the predictions for neutral atoms and atomic ions, and some homonuclear diatomic molecules. An account of fairly recent progress in obtaining the HF ionization potentials for the isoelectronic series of He, Be, Ne, Mg, and Arlike atomic ions is first considered. The 1= Z expansion for total nonrelativistic energy of atomic ions evokes that l52I is not very sensitive to the introduction of electron correlation. The connection between l and I for neutral atoms via the Pauli potential (VP) is then examined. We focus on the relation of VP to more recent advances in density functional theory (DFT) plus loworder density matrix theory. In this context, the example of nonrelativistic Belike atomic ions is treated. Afterward, we introduce the bosonized equation for the density amplitude ffiffiffi pq, which emphasizes the major role that plays dTW= dq in DFT. For spherical atomic densities, the bosonized potential argument strongly suggests also that l52I remains valid in the presence of electron correlation. Finally, numerical estimates of l and I from natural orbital functional (NOF) theory are presented for neutral atoms ranging from H to Kr. The predicted vertical I by means of the extended Koopmans' theorem are in good agreement with the corresponding experimental data. However, the NOF theory of l lowers the experimental values considerably as we approach to noble gas atoms though oscillatory behavior is in evidence. (C) 2015 Wiley Periodicals, Inc.   
Language 



English
 
Source (journal) 



International journal of quantum chemistry.  New York, N.Y.  
Publication 



Hoboken : Wileyblackwell, 2016
 
ISSN 



00207608
 
Volume/pages 



116:11(2016), p. 805818
 
ISI 



000374689200003
 
Full text (Publishers DOI) 


  
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