Comparative study between ab initio and semiempirical electrostatic potentials on molecular surfaces

The electrostatic potentials of 21 molecules containing different functional groups has been computed at the ab initio RHF/6‐31G* level on a series of solvent accessible surfaces and compared with MNDO, AM1, and PM3‐derived pontentials. We analyzed in detail the distribution of electrostatic potentials on the surfaces around their maximum and minimum values and found out that consistently MNDO gives results similar to ab initio potentials. The actual values of the MNDO electrostatic potentials show a systematic deviation from the “correct” results, but the pattern of the MEP distribution on the surface is similar to that of the ab initio results. In contrast, PM3 fails in some cases to give even the correct number or distribution of “hot spots” of potential (low MEP) on the surface. AM1 behaves somewhere between these two semiempirical methods. As a conclusion, MNDO would be suggested as the best approach to analyses requiring a fast and efficient mapping of electrostatic potentials on simplified models of molecular surfaces. © 1993 John Wiley & Sons, Inc.

[1]  Gustavo A. Arteca,et al.  Shape group studies of molecular similarity: relative shapes of Van der Waals and electrostatic potential surfaces of nicotinic agonists , 1988 .

[2]  Electrostatic potentials of tumour promoters , 1987 .

[3]  J. Stewart.  Optimization of parameters for semiempirical methods I. Method , 1989 .

[4]  C. Petrongolo,et al.  Ab initioLCAO-MO-SCF calculation of the electrostatic molecular potential of chlorpromazine and promazine , 1978 .

[5]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[6]  Joyce J. Kaufman,et al.  Electrostatic Molecular Potential Contour Maps from Ab-initio Calculations. 1. Biologically Significant Molecules. 2. Mechanism of Cationic Polymerization , 1981 .

[7]  Gábor Náray-Szabó.  Theoretical chemistry of biological systems , 1986 .

[8]  Methods for determining the reliability of semiempirical electrostatic potentials and potential derived charges , 1992 .

[9]  F. J. Luque,et al.  Comparative study of the molecular electrostatic potential obtained from different wavefunctions. Reliability of the semiempirical MNDO wavefunction , 1990 .

[10]  M. L. Connolly.  Solvent-accessible surfaces of proteins and nucleic acids. , 1983, Science.

[11]  K. Merz,et al.  Analysis of a large data base of electrostatic potential derived atomic charges , 1992 .

[12]  P. Dean,et al.  Molecular recognition: optimized searching through rotational 3-space for pattern matches on molecular surfaces , 1987 .

[13]  P. Goodford,et al.  Electrostatic potential and binding of drugs to the minor groove of dna , 1987 .

[14]  P. Mezey,et al.  A topological analysis of molecular electrostatic potential on van der Waals surfaces for histamine and 4‐substituted derivatives as H2‐receptor agonists , 1991 .

[15]  Laura Bonati,et al.  Molecular electrostatic potential of substituted aromatic compounds: Factors affecting the differences between Ab Initio and semiempirical results , 1992 .

[16]  M. Dewar,et al.  Ground States of Molecules. 38. The MNDO Method. Approximations and Parameters , 1977 .

[17]  L. Overman,et al.  Modeling chemical reactivity. 1. Regioselectivity of Diels-Alder cycloadditions of electron-rich dienes with electron-deficient dienophiles , 1986 .

[18]  Harel Weinstein,et al.  Analytical calculation of atomic and molecular electrostatic potentials from the Poisson equation , 1973 .

[19]  J. Stewart.  Optimization of parameters for semiempirical methods II. Applications , 1989 .

[20]  P. Kollman,et al.  Atomic charges derived from semiempirical methods , 1990 .

[21]  A. Chung-Phillips.  Deorthogonalization of atomic originals in the CNDO approach , 1989 .

[22]  Peter Politzer,et al.  Chemical Applications of Atomic and Molecular Electrostatic Potentials: "Reactivity, Structure, Scattering, And Energetics Of Organic, Inorganic, And Biological Systems" , 2013 .

[23]  Modesto Orozco,et al.  On the use of AM1 and MNDO wave functions to compute accurate electrostatic charges , 1990 .

[24]  P. Carrupt,et al.  Molecular electrostatic potentials for characterizing drug-biosystem interactions. , 1991, Methods in enzymology.

[25]  J. Murray,et al.  The use of the electrostatic potential at the molecular surface in recognition interactions: dibenzo-p-dioxins and related systems. , 1990, Journal of molecular graphics.

[26]  A. Gavezzotti,et al.  The calculation of molecular volumes and the use of volume analysis in the investigation of structured media and of solid-state organic reactivity , 1983 .