The Application of the Reaction-Field Method to the Calculation of Dielectric Constants

1998 ◽  
Vol 20 (3) ◽  
pp. 159-178 ◽  
Author(s):  
Jonathan W. Essex
Keyword(s):  
Field Method ◽  
Dielectric Constants ◽  
Reaction Field

Solvent and temperature effects on the tautomerization of a carbonitrile molecule: A conductor-like polarizable continuum model (CPCM) study

2021 ◽  
Vol 20 (1) ◽  
pp. 59-68
Author(s):  
Zohreh Khanjari ◽  
Bita Mohtat ◽  
Reza Ghiasi ◽  
Hoorieh Djahaniani ◽  
Farahnaz Kargar Behbahani
Keyword(s):  
Gas Phase ◽  
Solvent Effects ◽  
Continuum Model ◽  
Solvent Polarity ◽  
Polarizable Continuum Model ◽  
Dielectric Constants ◽  
Frontier Orbitals ◽  
Reaction Field ◽  
Polarizable Continuum ◽  
Homo Lumo

This research examined the effects of solvent polarity and temperature on the tautomerization of a carbonitrile molecule at CAM-B3LYP/6-311G (d,p) level of theory. The selected solvents were n-hexane, diethyl ether, pyridine, ethanol, methanol, and water. The solvent effects were examined by the self-consistent reaction field theory (SCRF) based on conductor-like polarizable continuum model (CPCM). The solvent effects were explored on the energy barrier, frontier orbitals energies, and HOMO-LUMO gap. Dependencies of thermodynamic parameters (ΔG and ΔH) on the dielectric constants of solvents were also tested. Specifically, the temperature dependencies of the thermodynamics parameters were studied within 100–1000 K range. The rate constant of the tautomerism reaction was computed from 300 to 1200 K, in the gas phase.

A multiconfigurational self‐consistent reaction‐field method

1988 ◽  
Vol 89 (5) ◽  
pp. 3086-3095 ◽  
Author(s):  
Kurt V. Mikkelsen ◽  
Hans Ågren ◽  
Hans Jo/rgen Aa. Jensen ◽  
Trygve Helgaker
Keyword(s):  
Field Method ◽  
Reaction Field ◽  
Self Consistent

The iterative self-consistent reaction-field method: The refractive index of pure water

2010 ◽  
Vol 111 (4) ◽  
pp. 904-913 ◽  
Author(s):  
Kristian O. Sylvester-Hvid ◽  
Kurt V. Mikkelsen ◽  
Mark A. Ratner
Keyword(s):  
Refractive Index ◽  
Pure Water ◽  
Field Method ◽  
Reaction Field ◽  
Self Consistent

scholarly journals Effect of the Reaction Field on Molecular Forces and Torques Revealed by an Image-Charge Solvation Model

2013 ◽  
Vol 13 (1) ◽  
pp. 129-149
Author(s):  
Wei Song ◽  
Yuchun Lin ◽  
Andrij Baumketner ◽  
Shaozhong Deng ◽  
Wei Cai ◽  
...  
Keyword(s):  
Dielectric Properties ◽  
Electrostatic Force ◽  
Chem Phys ◽  
Bulk Water ◽  
Dielectric Constants ◽  
Model Parameters ◽  
Image Charge ◽  
Solvation Model ◽  
Reaction Field ◽  
Charge Solvation

AbstractWe recently developed the Image-Charge Solvation Model (ICSM), which is an explicit/implicit hybrid model to accurately account for long-range electrostatic forces in molecular dynamics simulations [Lin et al., J. Chem. Phys., 131,154103,2009]. The ICSM has a productive spherical volume within the simulation cell for which key physical properties of bulk water are reproduced, such as density, radial distribution function, diffusion constants and dielectric properties. Although the reaction field (RF) is essential, it typically accounts for less than 2% of the total electrostatic force on a water molecule. This observation motivates investigating further the role of the RF within the ICSM. In this report we focus on distributions of forces and torques on water molecules as a function of distance from the origin and make extensive tests over a range of model parameters where Coulomb forces are decomposed into direct interactions from waters modeled explicitly and the RF. Molecular torques due to the RF typically account for 20% of the total torque, revealing why the RF plays an important role in the dielectric properties of simulated water. Moreover, it becomes clear that the buffer layer in the ICSM is essential to mitigate artifacts caused by the discontinuous change in dielectric constants at the explicit/implicit interface.

SOLVENT EFFECTS ON THE PROTON RESONANCE SPECTRA OF THE DICHLORO- AND DIBROMO-ETHYLENES: REACTION FIELD EFFECTS IN ALIPHATIC SOLVENTS AND SPECIFIC INTERACTIONS IN AROMATIC SOLVENTS

1963 ◽  
Vol 41 (12) ◽  
pp. 3034-3041 ◽  
Author(s):  
F. Hruska ◽  
E. Bock ◽  
T. Schaefer
Keyword(s):  
Field Effect ◽  
Dielectric Constants ◽  
Specific Interactions ◽  
Proton Resonance ◽  
Water Solutions ◽  
Reaction Field ◽  
Aromatic Solvents ◽  
Triple Bonds ◽  
Induced Dipole ◽  
Cis And Trans

The proton resonance shifts relative to internal cyclohexane and tetramethylsilane of cis and trans dichloro- and dibromo-ethylenes were measured in dioxane–water solutions, aliphatic solvents, and aromatic solvents. The dielectric constants of the dioxane–water solutions could be smoothly varied between 2 and 10 and, by taking Δ = cis–trans shifts as containing only the dipolar reaction field effect, the data for these solutions were treated as a test of the Buckingham reaction field equation. Linear plots were obtained and reasonable values of the coefficients of the E term confirmed the usefulness of this equation. An equation based on a nonspherical cavity was also used. It was also shown that quadrupolar reaction fields affected the proton shifts. Sizeable deviations from the dioxane–water standards were found for halogenated aliphatic solvents and those containing double or triple bonds. These deviations are interpreted in terms of the shape of the solute molecules and dispersion and anisotropic interactions. The much larger deviations found for aromatic solvents are harder to rationalize but specific interactions were found for both cis and trans forms, indicating an inadequacy in a simple dipole-induced dipole model.

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