A “critical” appraisal of electrostatic charge models for molecules

  • Shridhar R. Gadre
  • Savita S. Pundlik
  • Indira H. Shrivastava


The conventional electrostatic charge models (PD-AC) are constructed so as to reproduce the molecular electrostatic potential (MESP) on and beyond the van der Waals’ (vdW) surface. The MESP distribution has recently [S R Gadre, S A Kulkarni and I H Shrivastava (1992)J. Chem. Phys. 96 5253] been shown to exhibit rich topographical features. With this in view, a detailed topographical comparison of the MESP derived from the charge models, with the respectiveab initio (MO) ones is taken up for water, hydrogen sulphide, methane and benzene molecules as test cases. It is shown that the point charge models have a fundamental lacuna, viz. they fail to mimic the essential topographical features of MESP. A new model incorporating a small number of floating spherical Gaussians is shown to restore all the critical features of the molecules under study. A comparative study of the standard deviations of MESP derived from charge models on scaled vdW surfaces further reveals that the present model leads to a better representation ofab initio MESP.


Critical points topography electrostatics charge models 


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  1. Ahlrichs R, Bär M, Häser M and Kölmel C 1989Chem. Phys. Lett. 162 165CrossRefGoogle Scholar
  2. Bader R F W, Beddall P M and Cade P E 1971J. Am. Chem. Soc. 93 3095CrossRefGoogle Scholar
  3. Chipot C, Maigret B, Rivail J-L and Scheraga H A 1992J. Phys. Chem. 96 10276CrossRefGoogle Scholar
  4. Chirlian L E and Frand M M 1987J. Comput. Chem. 8 894CrossRefGoogle Scholar
  5. Coppens P, Guru Row T N, Leung P, Stevens E D, Becker P J and Yang Y W 1979Acta Crystallogr. A35 63Google Scholar
  6. Cox S R and Williams D E 1981J. Comput. Chem. 2 304CrossRefGoogle Scholar
  7. Ferenczy G G, Reynolds C A and Richards W G 1990J. Comput. Chem. 11 159CrossRefGoogle Scholar
  8. Gadre S R, Kölmel C and Shrivastava I H 1992aInorg. Chem. 31 2279CrossRefGoogle Scholar
  9. Gadre S R, Kulkarni S A and Shrivastava I H 1992bJ. Chem. Phys. 96 5253CrossRefGoogle Scholar
  10. Gadre S R and Pathak R K 1990Proc. Indian Acad. Sci. (Chem. Sci.) 102 189Google Scholar
  11. Gadre S R and Shrivastava I H 1991J. Chem. Phys. 94 4384CrossRefGoogle Scholar
  12. Gadre S R and Shrivastava I H 1993Chem. Phys. Lett. 204 350CrossRefGoogle Scholar
  13. Gadre S R and Taspa A 1993J. Mol. Graph. (in press)Google Scholar
  14. Gussoni M 1984J. Mol. Struct. 115 307CrossRefGoogle Scholar
  15. Hall G G 1986Int. J. Quantum Chem. 5 115Google Scholar
  16. Hobza P, Selzle H L and Schlag E W 1993J. Phys. Chem. 97 3937CrossRefGoogle Scholar
  17. Jorgensen W L 1979J. Am. Chem. Soc. 101 2011CrossRefGoogle Scholar
  18. Kubodera H, Nagakawa S and Umeyama H 1987Chem. Pharm. Bull. 35 1673Google Scholar
  19. Löwdin P-O 1950J. Chem. Phys. 18 365CrossRefGoogle Scholar
  20. Momany F A 1978J. Phys. Chem. 82 592CrossRefGoogle Scholar
  21. Mulliken R S 1955J. Chem. Phys. 23 1833CrossRefGoogle Scholar
  22. Naray-Szabo G 1993Chem. Design Autom. News 8 (May) 1Google Scholar
  23. Pietro W J, Francl M M, Hehre W J, Defrees D J, Pople J A and Binkley J S 1982J. Am. Chem. Soc. 104 5048CrossRefGoogle Scholar
  24. Reynolds C A, Essex J W and Richards W G 1992J. Am. Chem. Soc. 114 9075CrossRefGoogle Scholar
  25. Roterman I K, Gibson K D and Scheraga H A 1989J. Biomol. Struct. Dyn. 7 391Google Scholar
  26. Shirsat R N, Bapat S V and Gadre S R 1992Chem. Phys. Lett. 2 373CrossRefGoogle Scholar
  27. Shirsat R N, Limaye A C and Gadre S R 1993J. Comput. Chem. 14 445 (the parallel SCF package INDMOL, developed by S R Gadre and co-workers)CrossRefGoogle Scholar
  28. Singh U C and Kollman P A 1984J. Comp. Chem. 5 129CrossRefGoogle Scholar
  29. Sokalski W A, Shibata M, Ornstein R L and Rein R 1992J. Comput. Chem. 13 883CrossRefGoogle Scholar
  30. Synder L C and Basch H 1972Molecular wave functions and properties (New York: Wiley)Google Scholar
  31. Tomasi J, Bonaccorsi R and Cammi R 1991Theoretical models of chemical bonding Z B Maksic (Berlin, Heidelberg: Springer) Part 4Google Scholar
  32. Woods R J, Khalil M, Pell W, Moffat S H and Smith V H Jr 1990J. Comput. Chem. 11 297CrossRefGoogle Scholar
  33. Williams D E and Yan J M 1988Adv. At. Mol. Phys. 23 87CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 1994

Authors and Affiliations

  • Shridhar R. Gadre
    • 1
  • Savita S. Pundlik
    • 1
  • Indira H. Shrivastava
    • 1
  1. 1.Department of ChemistryUniversity of PoonaPuneIndia

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