Generic molecular mechanics as based on local quantum description of molecular electronic structure

Molecular mechanics (MM) is now widely used for modeling potential energy surfaces of large organic molecules. All MM schemes use ad hoc forms for the potential functions and parameters specially adjusted to fit experimental or quantum chemical data. In this work we attempt to deduce a generic MM scheme starting from a local quantum mechanical description of molecular electronic structure. The basis for this derivation is the trial electronic wave function in the form of antisymmetrized product of strictly localized geminals. The MM scheme obtained does not require adjusting any parameters. The quality of numerical estimates obtained by this scheme is analyzed. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002

[1]  Norman L. Allinger,et al.  Conformational analysis. 130. MM2. A hydrocarbon force field utilizing V1 and V2 torsional terms , 1977 .

[2]  Andrei L. Tchougréeff,et al.  Effective electronic Hamiltonian for quantum subsystem in hybrid QM/MM methods as derived from APSLG description of electronic structure of classical part of molecular system☆ , 2000 .

[3]  André Julg,et al.  The concept of the chemical bond , 1984 .

[4]  Robert G. Parr,et al.  Theory of Separated Electron Pairs , 1958 .

[5]  Norman L. Allinger,et al.  Molecular mechanics. The MM3 force field for hydrocarbons. 1 , 1989 .

[6]  Andreì L. Tchougréeff,et al.  Semiempirical implementation of strictly localized geminals for analysis of molecular electronic structure , 2001, J. Comput. Chem..

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

[8]  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.

[9]  A. L. Chugreev,et al.  SEMIEMPIRICAL ELECTRON PAIR CORRELATION METHOD FOR CALCULATION OF THE ELECTRONIC STRUCTURE OF MOLECULES , 1999 .

[10]  A. Tchougréeff,et al.  Effective Hamiltonian Approach to Catalytic Activity of Transition Metal Complexes , 2001 .

[11]  G. Náray-Szabó,et al.  Towards a molecular orbital method for the conformational analysis of very large biomolecules , 1976 .

[12]  Fernando Bernardi,et al.  Simulation of MC-SCF results on covalent organic multi-bond reactions: molecular mechanics with valence bond (MM-VB) , 1992 .

[13]  R. Mcweeny,et al.  Valence-Bond Calculations of the Potential-Energy Surface for CH4-)Ch3+h , 1994 .