Critical analysis of electric field modeling: Formamide

A detailed analysis of ab initio derived electric field and multipole modeling is presented using formamide as an example. Penetration effects, a problem encountered with most currently used modeling methods, are avoided using the Overlap Multipolar Expansion (OME) technique computed up to the hexadecapole level. This method is shown to be grid insensitive. The OME fields and subsequent atomic charge modeling are found to be more sensitive to correlation effects than to basis sets changes. Three different types of error analysis are applied to test the accuracy of regenerated fields from various multipole descriptions. It is shown that atom centered charge models, those most commonly used in the literature, have significant errors. Considerable improvement can be made by using various combinations of charge, dipole, and quadrupole atom‐ or bond‐centered models. For molecular dynamic programs it is argued that the best compromise between accuracy and efficiency is to use both atom and fictive atom charge models calculated from MP2 level density matrices using at least DZP level basis sets. © 1992 by John Wiley & Sons, Inc.

[1]  Donald E. Williams,et al.  Representation of the molecular electrostatic potential by a net atomic charge model , 1981 .

[2]  János G. Ángyán,et al.  Modelling the electric field of water obtained from accurate SCF wave functions , 1990 .

[3]  L. E. Chirlian,et al.  Atomic charges derived from electrostatic potentials: A detailed study , 1987 .

[4]  Donald E. Williams,et al.  Alanyl dipeptide potential‐derived net atomic charges and bond dipoles, and their variation with molecular conformation , 1990 .

[5]  M. J. D. Powell,et al.  Restart procedures for the conjugate gradient method , 1977, Math. Program..

[6]  R. Bader,et al.  Molecular fragments or chemical bonds , 1975 .

[7]  Donald E. Williams.  Representation of the molecular electrostatic potential by atomic multipole and bond dipole models , 1988 .

[8]  A. Hagler,et al.  Determination of atomic point charges and point dipoles from the Cartesian derivatives of the molecular dipole moment and second moments, and from energy second derivatives of planar dimers. II. Applications to model systems , 1989 .

[9]  Sarah L. Price,et al.  On the representation of electrostatic fields around ab initio charge distributions , 1991, J. Comput. Aided Mol. Des..

[10]  György G. Ferenczy.  Charges derived from distributed multipole series , 1991 .

[11]  Hans-Joachim Werner,et al.  PNO-CI and PNO-CEPA studies of electron correlation effects , 1976 .

[12]  C. Perrin,et al.  Atomic size dependence of Bader electron populations: significance for questions of resonance stabilization , 1991 .

[13]  Raymond A. Poirier,et al.  Cumulative atomic multipole representation of the molecular charge distribution and its basis set dependence , 1983 .

[14]  W. L. Jorgensen,et al.  The OPLS [optimized potentials for liquid simulations] potential functions for proteins, energy minimizations for crystals of cyclic peptides and crambin. , 1988, Journal of the American Chemical Society.

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

[16]  Robert J. Woods,et al.  Derivation of net atomic charges from molecular electrostatic potentials , 1990 .

[17]  R. Rein,et al.  Potential-derived point-charge model study of electrostatic interaction energies in some hydrogen-bonded systems. , 1985, International Journal of Quantum Chemistry.

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

[19]  J. A. C. Rullmann,et al.  Atomic charge models for polypeptides derived from ab initio calculations , 1989 .

[20]  A. Kuki,et al.  Partial charges by multipole constraint. Application to the amino acids , 1990 .

[21]  P. Claverie,et al.  The exact multicenter multipolar part of a molecular charge distribution and its simplified representations , 1988 .

[22]  A. T. Hagler,et al.  Determination of atomic point charges and point dipoles from the Cartesian derivatives of the molecular dipole moment and second moments, and from energy second derivatives of planar dimers. I. Theory , 1989 .

[23]  U. Singh,et al.  A combined ab initio quantum mechanical and molecular mechanical method for carrying out simulations on complex molecular systems: Applications to the CH3Cl + Cl− exchange reaction and gas phase protonation of polyethers , 1986 .

[24]  M. Karplus,et al.  CHARMM: A program for macromolecular energy, minimization, and dynamics calculations , 1983 .

[25]  Stefan Brode,et al.  Ab initio SCF calculations on low-energy conformers of N-acetyl-N'-methylalaninamide and N-acetyl-N'-methylglycinamide , 1991 .

[26]  Anthony J. Stone,et al.  Distributed multipole analysis, or how to describe a molecular charge distribution , 1981 .

[27]  György G. Ferenczy,et al.  Semiempirical AM1 electrostatic potentials and AM1 electrostatic potential derived charges: A comparison with ab initio values , 1989 .

[28]  U. Singh,et al.  A NEW FORCE FIELD FOR MOLECULAR MECHANICAL SIMULATION OF NUCLEIC ACIDS AND PROTEINS , 1984 .

[29]  U. Dinur.  Force related atomic multipoles in planar molecules. Derivation of atomic quadrupole and octupole moments , 1990 .

[30]  Robert L. Kuczkowski,et al.  Molecular structures of gas‐phase polyatomic molecules determined by spectroscopic methods , 1979 .

[31]  D. Pérahia,et al.  Use of the overlap multipole expansion for approximating molecular electrostatic potentials , 1979 .

[32]  P. Kollman,et al.  An all atom force field for simulations of proteins and nucleic acids , 1986, Journal of computational chemistry.