Theoretical Chemistry Accounts

, Volume 114, Issue 1–3, pp 38–45

About the Mulliken electronegativity in DFT

Article

Abstract

In the framework of density functional theory, a new formulation of electronegativity that recovers the Mulliken definition is proposed and its reliability is checked by computing electronegativity values for a large number of elements. It is found that the obtained values, which are compared with previously proposed electronegativity scales, fulfill the main periodic criteria.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Murphy LR, Meek TL, Allred AL, Allen LC (2000) J Phys Chem A 104:5867Google Scholar
  2. 2.
    (a) Pauling L (1932) J Am Chem Soc 54:3570; (b) Pauling L (1960) The nature of the chemical bond, 3rd edn. Cornell University Press, New York, pp 93Google Scholar
  3. 3.
    Mulliken RS (1934) J Chem Phys 2:782; ibid 3:573Google Scholar
  4. 4.
    Allred AL, Rochow EG (1958) J Inorg Nucl Chem 5:264Google Scholar
  5. 5.
    (a) Gordy W (1946) J Chem Phys 14:305; (b) Gordy W, Thomas WJO (1956) J Chem Phys 24:439Google Scholar
  6. 6.
    (a) Sanderson RT (1988) J Chem Ed 65:112; (b) Sanderson RT (1988) J Chem Ed 65:227; (c) Sanderson RT (1986) Inorg Chem 25:1858; (d) Sanderson RT (1986) Innorg Chem 25:3518; (e) Sanderson RT (1976) Chemical bonds and bond energy, 2nd edn.; Academic, New YorkGoogle Scholar
  7. 7.
    Iczkowski RP, Margrave JL (1961) J Am Chem Soc 83:3547Google Scholar
  8. 8.
    (a) Klopman G (1968) J Am Chem Soc 90:223; (b) Klopman G (1965) J Chem Phys 43:124Google Scholar
  9. 9.
    (a) Hinze J, Jaffé HH (1962) J Am Chem Soc 84:540; (b) Hinze J, Whitehead MA, Jaffé HH (1963) J Am Chem Soc 85:148; (c) Hinze J, Jaffé HH (1963) J Phys Chem 67:1501; (d) Hinze J (1968) Fortschr der Chem Forschung 9:448; (e) Hinze J, Jaffé HH (1963) Can J Chem 41:1315; (f) Bergmann D, Hinze J (1987) Struct and Bonding 66:145Google Scholar
  10. 10.
    (a) Mortier WJ, Ghosh SK, Shankar S (1986) J Am Chem Soc 108:4315; (b) Mortier W (1987) J Struct Bonding 66:125Google Scholar
  11. 11.
    (a) Parr RG, Donnelly RA, Levy M, Palke WE (1978) J Chem Phys 68:3801; (b) Parr RG, Bartolotti LJ (1993) J Am Chem Soc 104:3801; (c) Parr RG, Yang W (1989) Density Functional Theory of Atoms and Molecules; Oxford University Press: New York; (d) Chattaraj PK, Parr RG (1993) Structure and Bonding 80:11Google Scholar
  12. 12.
    Dreizler RM, da Providencia J (eds) (1985) Density functional methods in physics NATO ASI Series B, 123. Plenum Press, New YoryGoogle Scholar
  13. 13.
    Sen KD (ed) (1987) Electronegativity, Springer, Berlin Heidelberg New York vol 66Google Scholar
  14. 14.
    Huheey JE (1978) Inorganic chemistry. Principles of structure and reactivity, 2nd edn. Harper and Row, New YorkGoogle Scholar
  15. 15.
    Parr RG, Pearson RG (1983) J Am Chem Soc 105:7512Google Scholar
  16. 16.
    Bartolotti LJ, Gadre SR, Parr RG (1980) J Am Chem Soc 102:2945Google Scholar
  17. 17.
    Chermette H (1999) J Comp Chem 20:129Google Scholar
  18. 18.
    Geerlings P, De Proft F, Langenaeker W (2003) Chem Rev 103:1793Google Scholar
  19. 19.
    Pearson RG (1983) Struct and Bonding 80:1Google Scholar
  20. 20.
    (a) Kohn W, Becke AD, Parr RG (1996) J Phys Chem 100:1274; (b) Ayers PW, Parr RG (2000) J Am Chem Soc 122:2010; (c) Ayers PW, Parr RG (2001) J Am Chem Soc 123:2007Google Scholar
  21. 21.
    (a) Berkowitz M, Parr RG (1988) J Chem Phys 88:2554; (b) Ayers PW (2001) Theor Chem Acta 106:271; (c) Lovett R, Chung YM, Buff FP (1976) J Chem Phys 65:570; (d) Levy M, Perdew JP (1985) Phys Rev A 32:2010; (e) Garza J, Robles J (1993) Phys Rev A 47:2680Google Scholar
  22. 22.
    (a) Putz MV, Chiriac A, Mracec M (2001) Rev Roum Chim 46:1175; (b) Putz MV (2002) PhD Thesis, West University of Timisoara, RomaniaGoogle Scholar
  23. 23.
    Komorowski L (1987) Chem Phys 114:55Google Scholar
  24. 24.
    (a) Szasz L (1985) Pseudopotential theory of atoms and molecules. J Wiley, New York; (b) Preuss H (1969) Quantenchemie fuer Chemiker. Verlag Chemie, Weinheim; (c) Tables of pseudopotential data: http://indy2.theochem.uni-stuttgart.de and the foregoing references.
  25. 25.
    (a) March NH (1993) Struct Bond 80:71; (b) Sen KD (1993) Struct Bond 80:87Google Scholar
  26. 26.
    Pearson RG (1997) Chemical Hardness. Wiley-VCH Verlag: WeinheimGoogle Scholar
  27. 27.
    Tables of electronegativities: http://www.wellesley.edu/Chemistry/ chem241/en.html and the foregoing references
  28. 28.
    (a) Cao CZ, Li ZL, Allen LC (1999) Chin J Inorg Chem 15:218; (b) Allen LC (1994) Int J Quantum Chem 49:253; (c) Allen LC, Knight ET (1992) THEOCHEM 93:313; (d) Allen LC (1990) Acc Chem Res 23:175; (e) Allen LC, Huheey JE (1980) J Inorg Nuclear Chem 42:1523; (f) Allen LC (1989) J Am Chem Soc 111:9003Google Scholar
  29. 29.
    Bergmann D, Hinze J (1987) Struc and Bond 66:145Google Scholar
  30. 30.
    Putz MV, Russo N, Sicilia E (2003) J Phys Chem A 107:5461Google Scholar

Copyright information

© Springer-Verlag Berlin Heidelberg 2005

Authors and Affiliations

  1. 1.Dipartimento di Chimica and Centro di Calcolo ad Alte Prestazioni per Elaborazioni Parallele e Distribuite-Centro d'Eccellenza MIURUniversitá della CalabriaArcavacata di RendeItaly

Personalised recommendations