Abstract
A simple and fast method to calculate charge distributions in organic molecules is presented. The method is based on charge shifts within the saturated σ-system, driven by orbital electronegativities, coupled to a modified Hückel treatment of the unsaturated π-systems. Experimental molecular dipole moments of a set of 119 molecules are reproduced with a root mean square deviation of 0.36 Debye units. Furthermore, the obtained charge distribution is used to describe hydration free energies in terms of hydrogen-bonding donor and acceptor strengths of polar groups. Least square fitting to experimental data of 281 compounds leads to values for these strengths with accuracy limits of ±4.3% and ±2.5%, respectively. Properly normalized values are taken to parametrize the hydrogen bonding terms in our MAB force field. The method is sufficiently fast to be used in the preparatory phase of interactive force-field calculations.
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Li, J.H. and Allinger, N.L., J. Comput. Chem., 12 (1991) 186.
Brooks, B.R., Bruccoleri, R.E., Olafson, B.D., States, D.J., Swaminathan, S. and Karplus, M., J. Comput. Chem., 4 (1983) 187.
Momany, F.A., McGuire, R.F., Burgess, A.W. and Scheraga, H.A., J. Phys. Chem., 79 (1975) 2361.
Weiner, S.J., Kollman, P.A., Case, D.A., Singh, U.C., Ghio, C., Alagona, G., Profeta Jr., S. and Weiner, P., J. Am. Chem. Soc., 106 (1984) 765.
van Gunsteren, W.F. and Berendsen, H.J.C., GROMOS Library Manual, Biomos (1987) Nijenborgh 16, 9747 AG Groningen, The Netherlands.
Maple, J.R., Dinur, U. and Hagler, A.T., Proc. Natl. Acad. Sci. USA, 85 (1988) 5350.
Clark, M., Cramer III, R.D. and van Opdenbosch, N., J. Comput. Chem., 10 (1989) 982.
Momany, F.A. and Rone, R., J. Comput. Chem., 13 (1992) 888.
Breneman, C.M. and Wiberg, K.B., J. Comput. Chem., 11 (1989) 361.
Gasteiger, J. and Marsili, M., Tetrahedron, 36 (1980) 3219.
Gasteiger, J. and Saller, H., Angew. Chem. Int. Ed. Engl., 24 (1985) 687.
Rappé, A.K. and Goddard III, A., J. Phys. Chem., 95 (1991) 3358.
Winkler, R. and Pantelides, S.T., J. Chem. Phys., 106 (1997) 7714.
Abraham, R.J. and Grant, G.H., J. Comput.-Aided Mol. Design, 6 (1992) 273, and references therein.
Abraham, R.J., Warne, M.A. and Griffiths, L., J. Chem. Soc. Perkin Trans. 2, (1997) 881.
Lommerse, J.P.M., Price, S.L. and Taylor, R., J. Comput. Chem., 18 (1997) 757.
Wheatley, R.J. and Michell, J.O.B., J. Comput. Chem., 15 (1994) 1187.
Kollmann, P.A., J. Am. Chem. Soc., 100 (1978) 2974.
Vedani, A. and Dunitz, J.D., J. Am. Chem. Soc., 107 (1985) 7653.
Vinter, J.G., J. Comput.-Aided Mol. Design, 8 (1994) 653.
Vinter, J.G., J. Comput.-Aided Mol. Design, 8 (1996) 417.
Gerber, P. and Muller, K., J. Comput.-Aided Mol. Design, 6 (1995) 251.
Heilbronner, E. and Bock, H., The HMO Model and its Application, John Wiley & Sons, London, 1976.
Hinze, J., Whitehead, M.A. and Jaffé, H.H., J. Am. Chem. Soc., 85 (1963) 148.
Hinze, J. and Jaffé, H.H., J. Am. Chem. Soc., 84 (1962) 540.
Streitwieser, A., Molecular Orbital Theory for Organic Chemists, John Wiley, New York, NY, 1961.
Dewar, M.J.S., The Molecular Orbital Theory of Organic Chemistry, McGraw-Hill, New York, NY, 1969.
Callomon, J.H., Hirota, E., Kuchitsu, K., Lafferty, W.J., Maki, A.G. and Pote, C.S., In Hellwege, K.H. (Ed.) ‘Landold-Boernstein’, Vol.7, ‘Strukturdaten Freier Mehratomiger Molekeln’, Springer, Berlin, 1976.
McClellan, W.H., Tables of Experimental Dipole Moments, Freeman, San Francisco, CA, 1963.
Marynick, D.S., J. Comput. Chem., 18 (1997) 955.
Cabani, S., Gianni, P., Mollica, V. and Lepori, L., J. Sol. Chem., 10 (1981) 563.
Ooi, T., Oobatake, M., Nemethy, G. and Scheraga, H.A., Proc. Natl. Acad. Sci. USA, 84 (1987) 3086.
Ulmschneider, M., Ph. D. Thesis (1993). Université de Haute-Alsace, Strasbourg, France.
Curtiss, L.A., Frurip, D.J. and Blander, M., J. Chem. Phys., 71 (1979) 2703.
Quack, M. and Suhm, M.A., Theor. Chim. Acta, 93 (1996) 61.
Nelson, D.D., Fraser, G.T. and Klemperer, W., J. Chem. Phys., 87 (1985) 6364.
Berne, B.J. and Straub, J.E., Curr. Opin. Struct. Biol., 7 (1997) 181.
Raevsky, O.A., Grigorev, V.Y., Kireev, D.B. and Zefirov, N.S., Quant. Struct.-Act. Relatsh., 11 (1992) 49.
Raevsky, O.A., In Van de Waterbeemd H., Testa, B. and Folkers, G. (Eds.) Computer-Assisted Lead Finding and Optimization, Helvetica Chimica Acta, Basel, 1997, p. 367..
Wolfenden, R., Andersson, L., Cullis, P.M. and Southgate, C.C.B., Biochemistry, 20 (1981) 849.
Cullis, P.M. and Wolfenden, R., Biochemistry, 20 (1981) 3024.
Wolfenden, R., Liang, Y., Matthews, M. and Williams, R., J. Am. Chem. Soc., 109 (1987) 463.
Wolfenden, R. and Liang, Y., J. Biol. Chem., 263 (1988) 8022.
Gibbs, P.R., Radzicka, A. and Wolfenden, R., J. Am. Chem. Soc., 113 (1991) 4714.
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Gerber, P.R. Charge distribution from a simple molecular orbital type calculation and non-bonding interaction terms in the force field MAB. J Comput Aided Mol Des 12, 37–51 (1998). https://doi.org/10.1023/A:1007902804814
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DOI: https://doi.org/10.1023/A:1007902804814