Reaction field theory

Tapia, O. and O. Goscinski. 1975. Self-consistent reaction field theory of solvent effects. Mol. Phys. 29, 1653. 

We shall develop here a simple methodology for the computation of AEins, in terms of the electrostatic potential at nucleus V0. Within this frame, we will show that the first term of Eq (18) represents, in the context of the reaction field theory, the ion-solvent interaction energy. 

The Onsager s reaction field theory [3] has been incorporated into MO calculations by Tapia and Goscinski [6], The model has been applied to different problems using either semiempirical [51] or ab-initio MO theory [52], or correlated ab-initio techniques [52],... 

In this contribution, we describe and illustrate the latest generalizations and developments[1]-[3] of a theory of recent formulation[4]-[6] for the study of chemical reactions in solution. This theory combines the powerful interpretive framework of Valence Bond (VB) theory [7] — so well known to chemists — with a dielectric continuum description of the solvent. The latter includes the quantization of the solvent electronic polarization[5, 6] and also accounts for nonequilibrium solvation effects. Compared to earlier, related efforts[4]-[6], [8]-[10], the theory [l]-[3] includes the boundary conditions on the solute cavity in a fashion related to that of Tomasi[ll] for equilibrium problems, and can be applied to reaction systems which require more than two VB states for their description, namely bimolecular Sjy2 reactions ],[8](b),[12],[13] X + RY XR + Y, acid ionizations[8](a),[14] HA +B —> A + HB+, and Menschutkin reactions[7](b), among other reactions. Compared to the various reaction field theories in use[ll],[15]-[21] (some of which are discussed in the present volume), the theory is distinguished by its quantization of the solvent electronic polarization (which in general leads to deviations from a Self-consistent limiting behavior), the inclusion of nonequilibrium solvation — so important for chemical reactions, and the VB perspective. Further historical perspective and discussion of connections to other work may be found in Ref.[l],... 

Tapia, O. and Johannin, G. An inhomogeneous self-consistent reaction field theory of protein core effects. Towards a quantum scheme for describing enzyme reactions, J.Chem.Phys., 75 (1981), 3624-3635... 

Tapia, O., Colonna, F. and Angyan, J. G. Generalized self-consistent reaction field theory in multicenter-multipole ab initio LCGO framework. I. Electronic properties of the water molecule in a Monte Carlo sample of liquid water molecules studied with standard basis sets, J.ChimPhys., (1990), 875-903... 

Liu, Y.-P. and Newton, M. D. Solvent reorganization and donor/acceptor coupling in electron-transfer processes self-consistent reaction field theory and ab initio applications, J.Phys. Chem., 99 (1995), 12382-12386... 

Luhmer, M., Stein, M. L. and Reisse, J. Relative polarity of 1,3-dioxane and 1,4-dioxane studied by the reaction field theory and via computer simulations, Heterocycles, 37 (1994), 1041-1051... 

Sakurai M, Tamagawa H, Inoue Y, Ariga K, Kunitake T (1997) Theoretical study of intermolecular interaction at the lipid-water interface. 1. Quantum chemical analysis using a reaction field theory. J Phys Chem B 101 4810-4816... 

The reaction field theory is used96 to simulate the effect of the water environment the results on how couplings are affected by this medium effect are compatible with the known inhibition of the anomeric effect due to solvent dielectric influence. In this way, it is calculated that in methanol and methylamine only one-bond and 2J(H,H) and 2J(N,H) couplings are affected by the water environment. Changes in such couplings are dominated by the FC term. 

Initial supercritical fluid work was on C02 (21-23) and indicated weak interactions between the fluid and solute. Additional work has appeared on Xe, SF6, C2H, and NH3 (24,25). For all fluids, spectral shifts were observed with fluid density. Yonker, Smith and co-workers (24-26,28) compared their results to the McRae continuum model for dipolar solvation (56,57), which is based on Onsanger reaction field theory (58). Over a limited density range, there was agreement between the experimental data and the model (24-26,28), but conditions existed where the predicted linear relationship was not followed (28). At low fluid densities, this deviation was attributed (qualitatively) to fluid clustering around the solute (28). 

The Kamlet-Taft u polarity/polarizability scale is based on a linear solvation energy relationship between the n it transition energy of the solute and the solvent polarity ( 1). The Onsager reaction field theory (11) is applicable to this type of relationship for nonpolar solvents, and successful correlations have previously been demonstrated using conventional liquid solvents ( 7 ). The Onsager theory attempts to describe the interactions between a polar solute molecule and the polarizable solvent in the cybotatic region. The theory predicts that the stabilization of the solute should be proportional to the polarizability of the solvent, which can be estimated from the index of refraction. Since carbon dioxide is a nonpolar fluid it would be expected that a linear relationship... 

Reaction field theory with a spherical cavity, as proposed by Karlstrom [77, 78], has been applied to the calculation of the ECD spectrum of a rigid cyclic diamide, diazabicyclo[2,2,2]octane-3,6-dione, in an aqueous environment [79], In this case, the complete active space self-consistent field (CASSCF) and multiconfigurational second-order perturbation theory (CASPT2) methods were used. The qualitative shape of the solution-phase spectrum was reproduced by these reaction field calculations, although this was also approximately achieved by calculations on an isolated molecule. 

D. M. Chipman, Energy correction to simulation of volume polarization in reaction field theory, J. Chem. Phys., 116 (2002) 10129-10138. 

The solvent effects are often described within a semiempirical selfconsistent reaction field theory (SCRF)248. In this theory the free energy of solvation is obtained from a set of selfconsistent equations describing the interaction of the solute (denoted by S) with the solvent modeled by a polarizable continuum characterized by a dielectric constant e. In the SCRF formalism, as developed by Rivail and collaborators249- 250 the solute-solvent system is modeled by a polarizable continuum (characterized by a dielectric constant e) in which the solvent molecule is immersed within an ellipsoidal cavity251,252. The Hamiltonian describing the solute in the cavity is given by,... 

Wong MW, Wiberg KB, Frisch M (1991b) Hartree-Fock second derivatives and electric field properties in a solvent reaction field Theory and application. J Chem Phys 95 8991-8998... 

F. Self-Consistent Reaction Field Theory Using Ab Initio Methods.237... 

Wiberg and coworkers118 have described a similar study of 9b based on ab initio calculations and the reaction field theory. The resulting C=C barriers (Z - E) were around 30kcalmol 1, 9-10 kcal mol-1 higher than the experimental values (Table 2, Reference 40), but the difference between the barriers in o-dichlorobenzene and in A Af-dimethylformamide was well reproduced. 

Tel. 412-621-2050, fax 412-621-3563, e-mail info gaussian.com Gaussian 92. Ab initio molecular orbital calculations (Hartree-Fock, Direct HF, Moller-Plesset, Cl, Reaction Field Theory, electrostatic potential-derived charges, vibrational frequencies, etc.). Input and output of molecular structures in formats of many other molecular modeling systems. Browse for archival storage of computed results. VAX, Cray, DEC-RISC (Ultrix), Fujitsu (UXP/M), Kubota, IBM RS/6000, Multiflow, Silicon Graphics, Sun, and other versions. Gaussian 90 for Convex, FPS-500, Fujitsu (MSP), IBM (VM, MVS), HP-700, and NEC SX/3 systems. 

Donor/Acceptor Coupling of Electron Transfer Processes Self-Consistent Reaction Field Theory and Ab Initio Applications. 

Qualitatively, Eq. (4-32) predicts that the more dipolar isomer will be preferentially stabilized in more polar media. Quantitatively, the expression significantly overestimates the solvent effects obtained experimentally for conformational equilibria [182], Further modifications are necessary, e.g. adjustment for back-polarization of the solute by its own reaction field, inclusion of the effect of the solute s quadrupole moment on the reaction field [197], etc. Specific solute-solvent interactions, such as those with HBD solvents, cannot be treated with this reaction field theory. For a more detailed discussion, see references [83, 182]. 

According to the McRae-Bayliss model of solvatochromism [69, 70] which is directly evolved from Onsager s reaction field theory [80], the electronic transition from ground [g) to excited state (e) of a solvatochromic solute is given by Eq. (6-1) [318] ... 

The expression most commonly used in fluorescence spectroscopy is, however, the somewhat simphfied Eq. (6-5b), first developed by Lippert [47, 488] and Mataga [14, 489]. It is based on Onsager s reaction-field theory, which assumes that the fluorophore is a point dipole residing in the center of a spherical cavity with radius a in a homogeneous and isotropic dielectric with relative permittivity e,. The so-called Lippert-Mataga equation is as follows ... 

The first theoretical treatment of infrared solvent shifts was given in 1937 by Kirkwood [166] and by Bauer and Magat [167], Eq. (6-8) - known as the Kirkwood-Bauer-Magat (KBM) relationship - has been derived on the basis of Onsager s reaction field theory [80] using the simple model of a diatomic oscillator within a spherical cavity in an isotropic medium of macroscopic relative permittivity r. 

M. Sakurai, H. Tamagawa, Y. Inoue, K. Ariga, T. Kunitake, Theoretical Study of In-termolecular Interaction at the Lipid-Water Interface. 1. Quantum Chemical Analysis Using a Reaction Field Theory , J. Phys. Chem. B, 101, 4810 (1997)... 

O. Tapia, F. Colonna, and J. G. Angyan, ]. Chim. Phys., 87, 875 (1990). Generalized Self-Consistent Reaction Field Theory in a Multicenter-Multipole Ab Initio LCGO Framework. I. Electronic Properties of the Water Molecule in a Monte Carlo Sample of Liquid Water Molecules Studied with Standard Basis Sets. 

O. Tapia, /. Mol. Struct. (THEOCHEM), 226, 59 (1991). On the Theory of Solvent-Effect Representation. I. A Generalized Self-Consistent Reaction Field Theory. 

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