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Determination of the ionic radii by means of the Kohn–Sham potential: Identification of the chemical potential
Author(s) -
Barrera Mauricio,
Zuloaga Fernando
Publication year - 2006
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.20968
Subject(s) - ionization energy , ion , chemistry , ionic radius , ionic bonding , quantum chemical , atomic physics , radius , potential energy , ionization , computational chemistry , physics , molecule , organic chemistry , computer security , computer science
Under the Kohn–Sham theory, we examine solutions for the equations δ T S /δρ( r ) = 0 and δ T S /δρ( r ) = ν KS ( r ) that link the chemical potential of the electronic system with the effective Kohn–Sham potential through μ = ν KS ( r ) + δ T S /δρ. For single ions, we identify the chemical potential with the eigenvalue of the frontier orbital when the atom is in the limit of full ionization. For the case of cations, the chemical potential is found above −( I + A )/2 and has the property of grouping ions with the same chemical characteristics. For the anion instead, the chemical potential is fixed at the ionization energy. By solving the above equations numerically, two radial points called r − and r + are obtained and compared with the Shannon–Prewitt ionic radius. Moreover, we found for the halide series, that r − is numerically equivalent to rm , the radii where the electrostatic potential has its minimum, but shows different behavior upon charge variation. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006