Abstract
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.
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Ahlrichs R, Bär M, Häser M and Kölmel C 1989Chem. Phys. Lett. 162 165
Bader R F W, Beddall P M and Cade P E 1971J. Am. Chem. Soc. 93 3095
Chipot C, Maigret B, Rivail J-L and Scheraga H A 1992J. Phys. Chem. 96 10276
Chirlian L E and Frand M M 1987J. Comput. Chem. 8 894
Coppens P, Guru Row T N, Leung P, Stevens E D, Becker P J and Yang Y W 1979Acta Crystallogr. A35 63
Cox S R and Williams D E 1981J. Comput. Chem. 2 304
Ferenczy G G, Reynolds C A and Richards W G 1990J. Comput. Chem. 11 159
Gadre S R, Kölmel C and Shrivastava I H 1992aInorg. Chem. 31 2279
Gadre S R, Kulkarni S A and Shrivastava I H 1992bJ. Chem. Phys. 96 5253
Gadre S R and Pathak R K 1990Proc. Indian Acad. Sci. (Chem. Sci.) 102 189
Gadre S R and Shrivastava I H 1991J. Chem. Phys. 94 4384
Gadre S R and Shrivastava I H 1993Chem. Phys. Lett. 204 350
Gadre S R and Taspa A 1993J. Mol. Graph. (in press)
Gussoni M 1984J. Mol. Struct. 115 307
Hall G G 1986Int. J. Quantum Chem. 5 115
Hobza P, Selzle H L and Schlag E W 1993J. Phys. Chem. 97 3937
Jorgensen W L 1979J. Am. Chem. Soc. 101 2011
Kubodera H, Nagakawa S and Umeyama H 1987Chem. Pharm. Bull. 35 1673
Löwdin P-O 1950J. Chem. Phys. 18 365
Momany F A 1978J. Phys. Chem. 82 592
Mulliken R S 1955J. Chem. Phys. 23 1833
Naray-Szabo G 1993Chem. Design Autom. News 8 (May) 1
Pietro W J, Francl M M, Hehre W J, Defrees D J, Pople J A and Binkley J S 1982J. Am. Chem. Soc. 104 5048
Reynolds C A, Essex J W and Richards W G 1992J. Am. Chem. Soc. 114 9075
Roterman I K, Gibson K D and Scheraga H A 1989J. Biomol. Struct. Dyn. 7 391
Shirsat R N, Bapat S V and Gadre S R 1992Chem. Phys. Lett. 2 373
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)
Singh U C and Kollman P A 1984J. Comp. Chem. 5 129
Sokalski W A, Shibata M, Ornstein R L and Rein R 1992J. Comput. Chem. 13 883
Synder L C and Basch H 1972Molecular wave functions and properties (New York: Wiley)
Tomasi J, Bonaccorsi R and Cammi R 1991Theoretical models of chemical bonding Z B Maksic (Berlin, Heidelberg: Springer) Part 4
Woods R J, Khalil M, Pell W, Moffat S H and Smith V H Jr 1990J. Comput. Chem. 11 297
Williams D E and Yan J M 1988Adv. At. Mol. Phys. 23 87
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Gadre, S.R., Pundlik, S.S. & Shrivastava, I.H. A “critical” appraisal of electrostatic charge models for molecules. Proc. Indian Acad. Sci. (Chem. Sci.) 106, 303–314 (1994). https://doi.org/10.1007/BF02840752
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DOI: https://doi.org/10.1007/BF02840752