Skip to main content
SpringerLink
Log in

Toward a semiempirical density functional theory of chemical binding

  • Published:
Theoretica chimica acta Aims and scope Submit manuscript

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.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References and notes

  1. Parr RG (1983) Ann Rev Phys Chem 34:631

    Google Scholar 

  2. Dreizler RM, da Providencia J (1975) Density functional methods in physics. Plenum Press, New York

    Google Scholar 

  3. Parr RG, Donnelly RA, Levy M, Palke WE (1978) J Chem Phys 68:3801

    Google Scholar 

  4. Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512

    Google Scholar 

  5. Pearson RG (1985) J Am Chem Soc 107:6801

    Google Scholar 

  6. Berkowitz M, Ghosh SK, Parr RG (1985) J Am Chem Soc 107:6811

    Google Scholar 

  7. Yang W, Parr RG (1985) Proc Natl Acad Sci 82:6723

    PubMed  Google Scholar 

  8. Parr RG, Yang W (1984) J Am Chem Soc 106:4049; Yang W, Parr RG, Pucci R (1984) J Chem Phys 81:2862

    Google Scholar 

  9. 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:

    PubMed  Google Scholar 

  10. Parr RG, Rupnik K, Ghosh SK (1986) Phys Rev Lett 56:1555;

    PubMed  Google Scholar 

  11. Ghosh SK, Parr RG (1986) Phys Rev A 34:785

    PubMed  Google Scholar 

  12. Hall GG (1985) Adv Atom Molec Phys 20:41

    Google Scholar 

  13. Sanderson RT (1951) Science 114:670

    Google Scholar 

  14. Mortier WJ, Van Genechten K, Gasteiger J (1985) J Am Chem Soc 107:829

    Google Scholar 

  15. 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

    Google Scholar 

  16. For point charge models involving lone pairs as point charges see Kollman P (1978) J Am Chem Soc 100:2974

    Google Scholar 

  17. Sanderson RT (1976) Chemical bonds and bond energies (2nd edn). Academic Press, New York; Sanderson RT (1983) J Am Chem Soc 105:2259

    Google Scholar 

  18. Evans RS, Huheey JE (1970) J Inorg Nucl Chem 32:777

    Google Scholar 

  19. Rudenberg K (1962) Rev Mod Phys 34:326

    Google Scholar 

  20. 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

    Google Scholar 

  21. Politzer P, Weinstein H (1979) J Chem Phys 71:4218

    Google Scholar 

  22. Parr RG, Bartolotti LJ (1982) J Am Chem Soc 104:3801

    Google Scholar 

  23. Parr RG, Borkman RF (1968) J Chem Phys 49:1055

    Google Scholar 

  24. Borkman RF, Simons G, Parr RG (1969) J Chem Phys 50:58

    Google Scholar 

  25. Simons G, Parr RG (1971) J Chem Phys 55:4197

    Google Scholar 

  26. Politzer P (1970) J Chem Phys 52:2157

    Google Scholar 

  27. Pasternak A (1977) J Chem Phys 26:101

    Google Scholar 

  28. Pasternak A (1980) J Chem Phys 73:593

    Google Scholar 

  29. Ray NK, Samuels L, Parr RG (1979) J Chem Phys 70:3680

    Google Scholar 

  30. Politzer P (1969) J Chem Phys 50:2780; Politzer P (1969) J Chem Phys 51:459

    Google Scholar 

  31. Coulson CA, O'Leary B, Mallion RB (1978) Hückel theory for organic chemists. Academic Press, London

    Google Scholar 

  32. Parr RG (1963) Quantum theory of molecular electronic structure. Benjamin, New York

    Google Scholar 

  33. Nalewajski RF (1985) J Phys Chem 89:2831; see also: Nalewajski RF, Koninski M (1984) J Phys Chem 88:6234

    Google Scholar 

  34. 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

    Google Scholar 

  35. Politzer P, Parr RG, Murphy DR (1983) J Chem Phys 79:3859

    Google Scholar 

  36. Klopman G (1964) J Am Chem Soc 86:1463

    Google Scholar 

  37. Streitwieser A (1960) J Am Chem Soc 82:4123

    Google Scholar 

  38. Politzer P (1968) Trans Faraday Soc 64:2241

    Google Scholar 

  39. 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

    Google Scholar 

  40. For example: Zerner MC, Parr RG (1978) J Chem Phys 69:3858

    Google Scholar 

  41. Yang W, Lee C, Ghosh SK (1985) J Chem Phys 89:5412

    Google Scholar 

  42. Ohwada K (1982) J Chem Phys 77:5040

    Google Scholar 

  43. Ohwada K (1984) J Chem Phys 80:1556

    Google Scholar 

  44. Zangwill A, Levine ZH (1985) Am J Phys 53:1177

    Google Scholar 

  45. Aslaksen EW (1972) Phys Rev A 6:1367

    Google Scholar 

  46. Phillips JC (1969) Covalent bonding in crystals, molecules and polymers. University of Chicago Press, Chicago

    Google Scholar 

  47. 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

    Google Scholar 

  48. 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

    Google Scholar 

  49. 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

    Google Scholar 

Download references

Author information

Author notes

  1. Swapan K. Ghosh

    Present address: Heavy Water Division, Bhabha Atomic Research Centre, 400085, Bombay, India

Authors and Affiliations

  1. Department of Chemistry, University of North Carolina, 27514, Chapel Hill, NC, USA

    Swapan K. Ghosh & Robert G. Parr

Authors
  1. Swapan K. Ghosh
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Robert G. Parr
    View author publications

    You can also search for this author in PubMed Google Scholar

Additional information

Dedicated to Professor J. Koutecký on the occasion of his 65th birthday

Rights and permissions

Reprints and permissions

About this article

Cite this article

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

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1007/BF01192230

Key words

Search

Navigation