Abstract
The new ideas ofbond electronegativity andbond hardness are introduced, and a semiempirical density functional approach to the theory of molecular electronic structure and chemical binding is outlined. There result effective electronegativity equalization procedures that permit calculation of binding energies as well as partial charges. By a modelling of the bond electronegativity and bond hardness, a density functional interpretation of earlier bond charge models is established. Some numerical results are given for diatomic molecules.
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Parr RG (1983) Ann Rev Phys Chem 34:631
Dreizler RM, da Providencia J (1975) Density functional methods in physics. Plenum Press, New York
Parr RG, Donnelly RA, Levy M, Palke WE (1978) J Chem Phys 68:3801
Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512
Pearson RG (1985) J Am Chem Soc 107:6801
Berkowitz M, Ghosh SK, Parr RG (1985) J Am Chem Soc 107:6811
Yang W, Parr RG (1985) Proc Natl Acad Sci 82:6723
Parr RG, Yang W (1984) J Am Chem Soc 106:4049; Yang W, Parr RG, Pucci R (1984) J Chem Phys 81:2862
Ghosh SK, Berkowitz M, Parr RG (1984) Proc Natl Acad Sci USA 81:8028; Ghosh SK, Berkowitz M (1985) J Chem Phys. 83:2976; practical computational advantages of these formalisms for calculation of Compton profiles and exchange energies can be found in:
Parr RG, Rupnik K, Ghosh SK (1986) Phys Rev Lett 56:1555;
Ghosh SK, Parr RG (1986) Phys Rev A 34:785
Hall GG (1985) Adv Atom Molec Phys 20:41
Sanderson RT (1951) Science 114:670
Mortier WJ, Van Genechten K, Gasteiger J (1985) J Am Chem Soc 107:829
Mortier WJ (1987) In: Sen KD (ed) Electronegativity (Structure and bending, vol 66). Springer, Berlin Heidelberg, New York; Mortier WJ, Ghosh SK, Shankar S (1986) J Am Chem Soc 108:4315
For point charge models involving lone pairs as point charges see Kollman P (1978) J Am Chem Soc 100:2974
Sanderson RT (1976) Chemical bonds and bond energies (2nd edn). Academic Press, New York; Sanderson RT (1983) J Am Chem Soc 105:2259
Evans RS, Huheey JE (1970) J Inorg Nucl Chem 32:777
Rudenberg K (1962) Rev Mod Phys 34:326
The term bond electronegativity has been used earlier to denote electronegativity of orbitals forming the chemical bond: Hinze J, Whitehead MA, Jaffe HH (1963) J Am Chem Soc 85:148; see also Pritchard HO (1963) J Am Chem Soc 85:1876
Politzer P, Weinstein H (1979) J Chem Phys 71:4218
Parr RG, Bartolotti LJ (1982) J Am Chem Soc 104:3801
Parr RG, Borkman RF (1968) J Chem Phys 49:1055
Borkman RF, Simons G, Parr RG (1969) J Chem Phys 50:58
Simons G, Parr RG (1971) J Chem Phys 55:4197
Politzer P (1970) J Chem Phys 52:2157
Pasternak A (1977) J Chem Phys 26:101
Pasternak A (1980) J Chem Phys 73:593
Ray NK, Samuels L, Parr RG (1979) J Chem Phys 70:3680
Politzer P (1969) J Chem Phys 50:2780; Politzer P (1969) J Chem Phys 51:459
Coulson CA, O'Leary B, Mallion RB (1978) Hückel theory for organic chemists. Academic Press, London
Parr RG (1963) Quantum theory of molecular electronic structure. Benjamin, New York
Nalewajski RF (1985) J Phys Chem 89:2831; see also: Nalewajski RF, Koninski M (1984) J Phys Chem 88:6234
Nakatsuji H, Koga T (1981) In: Deb BM (ed) The force concept in chemistry. Van Nostrand and Reinhold, New York; see also: Simons G (1972) J Chem Phys 56:4310
Politzer P, Parr RG, Murphy DR (1983) J Chem Phys 79:3859
Klopman G (1964) J Am Chem Soc 86:1463
Streitwieser A (1960) J Am Chem Soc 82:4123
Politzer P (1968) Trans Faraday Soc 64:2241
For a discussion of kinetic energy in Hückel method see: Pucci R, March NH (1981) J Chem Phys Phys 74:2936; see also: Henderson GA, Parr RG (1971) Theor Chim Acta 31:103
For example: Zerner MC, Parr RG (1978) J Chem Phys 69:3858
Yang W, Lee C, Ghosh SK (1985) J Chem Phys 89:5412
Ohwada K (1982) J Chem Phys 77:5040
Ohwada K (1984) J Chem Phys 80:1556
Zangwill A, Levine ZH (1985) Am J Phys 53:1177
Aslaksen EW (1972) Phys Rev A 6:1367
Phillips JC (1969) Covalent bonding in crystals, molecules and polymers. University of Chicago Press, Chicago
Benson SW (1978) Angew Chem Int Ed Eng 17:812; Benson SW, Luria M (1975) J Am Chem Soc 97:704, 3337; Luria M, Benson SW (1975) J Am Chem Soc 97:3342
The term “geminal electronegativity” has been earlier proposed by Ferreira R (1967) Adv Chem Phys 13:55 (see p 73). This concept is being further studied in this laboratory
Coulson CA, Longuet-Higgins HC (1947) Proc Roy Soc A 191:39; Chirgwin BH, Coulson CA (1950) Proc Roy Soc A 201:196; Longuet-Higgins HC, Wheland GW (1950) Ann Rev Phys Chem 1:133
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Dedicated to Professor J. Koutecký on the occasion of his 65th birthday
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Ghosh, S.K., Parr, R.G. Toward a semiempirical density functional theory of chemical binding. Theoret. Chim. Acta 72, 379–391 (1987). https://doi.org/10.1007/BF01192230
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DOI: https://doi.org/10.1007/BF01192230