Local Field Representation of Surrounding Medium Effects. From Liquid Solvent to Protein Core Effects

An effective Schrodinger equation describing a small portion of a larger (macroscopic) system is derived from a general quantum/statistical mechanical approach. Only electrostatic interactions are allowed for between the subsystem. The effect of the environment (large position) on the solute (small position) is represented with a temperature dependent electrostatic potential. It is shown that, in general, this potential depends on the electronic wave function of the solute. This feature leads to a non-linear Schrodlnger equation. The non-linearity is being represented via the. moments of the. solute electronic density. In thu manner an adequate, framework is worked out which permits the. discussion of several local field theories of solvent effects that would otherwise Amain as singular models. A description of systems as digerent as diluted Liquid, solid or matrix solutions, defaults in crystalline environments, solvated electrons, and reactive subsystems in globular proteins can be given within this rather flexible theoretical approach.

[1]  Orlando Tapia,et al.  Self-consistent reaction field theory of solvent effects , 1975 .

[2]  B. Rode,et al.  Potential Curves for Proton Transfer Along Hydrogen Bonds , 1974 .

[3]  S. Miertus,et al.  Quantum-Chemical study of radical ions and molecules incorporating solvent effect.: I. Solvent effect within the π (PPP-like) and CNDO methods , 1977 .

[4]  F. Harris.  Self‐Consistent Methods in Hückel Theory , 1968 .

[5]  J. Kirkwood,et al.  Theory of Solutions of Molecules Containing Widely Separated Charges with Special Application to Zwitterions , 1934 .

[6]  Daniel Rinaldi,et al.  Polarisabilites moléculaires et effet diélectrique de milieu à l'état liquide. Étude théorique de la molécule d'eau et de ses diméres , 1973 .

[7]  G. G. Hall,et al.  The development of quantum mechanical solvent effect models. Macroscopic electrostatic contributions , 1976 .

[8]  J. Spanget-Larsen.  Structure and solvation of nitrobenzene and 1,4-dinitrobenzene radical anions , 1979, Theoretica chimica acta.

[9]  S. Yomosa.  Nonlinear Schrödinger Equation on the Molecular Complex in Solution –Towards a Biophysics– , 1973 .

[10]  Harold L. Friedman,et al.  Image approximation to the reaction field , 1975 .

[11]  A. Warshel.  A microscopic model for calculations of chemical processes in aqueous solutions , 1978 .

[12]  B. Pullman.  Environmental Effects on Molecular Structure and Properties , 1975 .

[13]  J. Spanget-Larsen.  Solvation of the nitrobenzene radical anion , 1976 .

[14]  K. Morokuma,et al.  A fractional charge model in the molecular orbital theory and its application to molecules in solutions and solids , 1976 .

[15]  B. Pullman,et al.  Chemical and biochemical reactivity , 1975 .

[16]  S. Yomosa.  On the Basic Equation for the Equilibrium Electronic States in Polar Solvents —Broken Symmetry— , 1978 .

[17]  G. G. Hall,et al.  A model for the ab initio calculation of some solvent effects , 1974 .

[18]  J. Bardeen.  The Image and Van der Waals Forces at a Metallic Surface , 1940 .

[19]  R. Constanciel,et al.  On the theory of solvent effects , 1978 .

[20]  A. Warshel,et al.  Energetics of enzyme catalysis. , 1978, Proceedings of the National Academy of Sciences of the United States of America.

[21]  Solvent interaction within the Hartree-Fock SCF molecular orbital formalism , 1974 .

[22]  O. Tapia,et al.  A quantum chemical study of solvent effects on biomolecules: an application of the virtual charge model and the self-consistent reaction field theory of solvent effect to γ-amino butyric acid, β-alanine and glycine , 1979 .

[23]  O. Tapia,et al.  Environmental effects on H-bond potentials: A SCRF MO CNDO/2 study of some model systems. , 1978, Journal of theoretical biology.

[24]  K. Fukui,et al.  An MO-theoretical calculation of solvent effect upon the NH3 + HF = NH4F reaction , 1973 .

[25]  W G Hol,et al.  On the role of the active site helix in papain, an ab initio molecular orbital study. , 1979, Biophysical chemistry.

[26]  B. L. Burrows,et al.  Solvent-Shift Effects on Electronic Spectra and Excited-State Dipole Moments and Polarizabilities , 1973 .

[27]  M. Hasegawa,et al.  Valence Bond Study of the Hydrogen Bond. III. Formation and Migration of Ionic Defects in Water and Ice , 1970 .

[28]  J. S. Kwiatkowski,et al.  A simple electrostatic model of solvation for large molecules within the SCF MO theory , 1978 .

[29]  J. Spanget-Larsen.  INDO Calculations with inclusion of an effective solvent field. Application to benzosemiquinones , 1978 .

[30]  C. Herrmann,et al.  Theoretical study of the shifts of electronic spectra from solute-solvent interaction , 1977 .

[31]  M. Born.  Volumen und Hydratationswärme der Ionen , 1920 .

[32]  David L. Beveridge,et al.  Approximate molecular orbital theory , 1970 .

[33]  W. P. Weijland,et al.  Reduction potentials of various aromatic hydrocarbons and their univalent anions , 1956 .

[34]  M. Levitt,et al.  Theoretical studies of enzymic reactions: dielectric, electrostatic and steric stabilization of the carbonium ion in the reaction of lysozyme. , 1976, Journal of molecular biology.

[35]  P. Fontana.  Theory of Long-Range Interatomic Forces. I. Dispersion Energies between Unexcited Atoms , 1961 .

[36]  G. Johannin,et al.  An estimate of intraproteic electrostatic fields values originated by the peptide groups in -chymotrypsin. , 1972, Biochemical and biophysical research communications.

[37]  J. Lennard-jones,et al.  Processes of adsorption and diffusion on solid surfaces , 1932 .

[38]  J. D. Ramshaw.  On the reduction of many‐body dielectric theories to the Onsager equation , 1974 .

[39]  G. Klopman.  Solvations: a semi-empirical procedure for including solvation in quantum mechanical calculations of large molecules , 1967 .

[40]  K. S. Raghuveer,et al.  On the Development of Solvent Effect Models: Method Development and Initial Applications , 1976 .

[41]  Jean-Louis Rivail,et al.  A quantum chemical approach to dielectric solvent effects in molecular liquids , 1976 .

[42]  O. Tapia,et al.  Medium polarization effect on proton potential shape S.A SCRF--MO CNDO/2 study of methanol and methanethiol H-bonded to imidazol. , 1978, Biochemical and biophysical research communications.

[43]  M. Barfield,et al.  Solvent dependence of nuclear spin-spin coupling constants , 1973 .

[44]  W. G. Laidlaw,et al.  On the application of the variational principle to a type of nonlinear ’’Schrödinger equation’’ , 1979 .