caa a22 4500 467893179 CHVBK 20180406152754.0 cr unu---uuuuu 170328e20061201xx s 000 0 eng 10.1007/s10955-006-9031-0 doi (NATIONALLICENCE)springer-10.1007/s10955-006-9031-0 On Hardness and Electronegativity Equalization in Chemical Reactivity Theory [Elektronische Daten] [Morrel Cohen, Adam Wasserman] Chemical Reactivity Theory (CRT) contains reactivity indices defined as first and second derivatives of ground-state properties with respect to electron number such as the electronegativity and the hardness. This necessitates use of the Perdew, Parr, Levy, and Balduz (PPLB) version of noninteger density-functional theory (NIDFT) to provide a basis for CRT in DFT. However, the PPLB NIDFT yields ground-state properties which are piecewise linear continuous functions of number, yielding vanishing hardness and staircase electronegativities which do not admit electronegativity equalization. To overcome these difficulties, in the present paper we modify the relationship between CRT and DFT, basing the former on our previously formulated "atoms” in "molecules” theory (AIMT) but retaining the PPLB NIDFT. We recapture electronegativity equalization through the agency of a uniquely defined reactivity potential. We demonstrate that a positive definite hardness matrix can be defined which controls the minimum cost to the AIMT energy functional of internal fluctuations of the electron numbers of the parts of a system. Springer Science+Business Media, Inc., 2006 Chemical reactivity theory nationallicence hardness nationallicence electronegativity nationallicence DFT nationallicence AIMT : "Atoms” in "Molecules” theory nationallicence CP : Car-Parinello(28) nationallicence CRT : Chemical-reactivity theory nationallicence DF : Density functional nationallicence DFT : Density-functional theory nationallicence EDF : Ensemble density functional nationallicence EDFT : Ensemble density-functional theory nationallicence EEP : Electronegativity equalization principle nationallicence EVR : Ensemble v-representable nationallicence HK : Hohenberg-Kohn(1) nationallicence HOMO : Highest occupied molecular orbital nationallicence KS : Kohn-Sham(2) nationallicence LL : Levy-Lieb constrained search algorithm(11-13) nationallicence LUMO : Lowest unoccupied molecular orbital nationallicence NIDF : Non-integer density functional nationallicence NIDFT : Non-integer density-functional theory nationallicence PPLB : Perdew Parr Levy and Balduz(9) nationallicence Cohen Morrel Department of Physics and Astronomy, Rutgers University, 126 Frelinghuysen Rd., 08854, Piscataway, NJ, USA aut Wasserman Adam Department of Chemistry and Chemical Biology, Rutgers University, 610 Taylor Rd., 08854, Piscataway, NJ, USA aut Journal of Statistical Physics Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 125/5-6(2006-12-01), 1121-1139 0022-4715 125:5-6<1121 2006 125 10955 https://doi.org/10.1007/s10955-006-9031-0 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s10955-006-9031-0 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- Cohen Morrel Department of Physics and Astronomy, Rutgers University, 126 Frelinghuysen Rd., 08854, Piscataway, NJ, USA aut NATIONALLICENCE 700 1- Wasserman Adam Department of Chemistry and Chemical Biology, Rutgers University, 610 Taylor Rd., 08854, Piscataway, NJ, USA aut NATIONALLICENCE 773 0- Journal of Statistical Physics Kluwer Academic Publishers-Plenum Publishers; http://www.springer-ny.com 125/5-6(2006-12-01), 1121-1139 0022-4715 125:5-6<1121 2006 125 10955 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer