Continuum-Model Treatment of Long-Range Intermolecular Forces. I. Pure Substances

Linder, Bruno

doi:10.1063/1.1731235

Cited by 71 publications

(23 citation statements)

References 11 publications

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“…[10][11][12][14][15][16] There have been several attempts to evaluate electrostatic, dispersion, and repulsion contributions to DG sol simultaneously, so that all these forces contribute self-consistently to the solute charge redistribution that takes place upon solvation. The basic formalism in this approach was outlined by Linder, [27][28][29] who made use of the solvent fluctuating reaction potential and its effect on the solute polarizability, and has been later implemented into different QM-SCRF continuum formalisms, [30][31][32][33][34][35][36][37][38] thus providing a theoretical framework to examine the influence of the mutual coupling between electrostatic, dispersion, and repulsion components on the properties of the solute in liquid environments.…”

Section: Introductionmentioning

confidence: 99%

Dispersion and repulsion contributions to the solvation free energy: Comparison of quantum mechanical and classical approaches in the polarizable continuum model

Curutchet¹,

Orozco²,

Luque³

et al. 2006

J Comput Chem

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We report a systematic comparison of the dispersion and repulsion contributions to the free energy of solvation determined using quantum mechanical self-consistent reaction field (QM-SCRF) and classical methods. In particular, QM-SCRF computations have been performed using the dispersion and repulsion expressions developed in the framework of the integral equation formalism of the polarizable continuum model, whereas classical methods involve both empirical pairwise potential and surface-dependent approaches. Calculations have been performed for a series of aliphatic and aromatic compounds containing prototypical functional groups in four solvents: water, octanol, chloroform, and carbon tetrachloride. The analysis is focused on the dependence of the dispersion and repulsion components on the level of theory used in QM-SCRF computations, the contribution of those terms in different solvents, and the magnitude of the coupling between electrostatic and dispersion-repulsion components. Finally, comparison is made between the dispersion-repulsion contributions obtained from QM-SCRF calculations and the results determined from classical approaches.

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Section: Introductionmentioning

confidence: 99%

Dispersion and repulsion contributions to the solvation free energy: Comparison of quantum mechanical and classical approaches in the polarizable continuum model

Curutchet¹,

Orozco²,

Luque³

et al. 2006

J Comput Chem

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“…In the cases considered in ref. 1 dispersion interactions gave the dominant contribution to intermolecular interactions. In the present work, further developments in the application of the method are introduced, and the calculations on liquid water illustrate the importance of the dipolar term.…”

Section: Introductionmentioning

confidence: 99%

Continuum reaction field calculation of dielectric constant and vapor pressures for water and carbon disulfide

Nir¹

1976

Biophysical Journal

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Continuum reaction field theory is applied to calculations of dielectric constant, contribution of intermolecular interactions to the free energy of a liquid, and heat of vaporization. Introduction of repulsive interactions and the use of one adjustable parameter, the free volume, enables prediction of vapor pressures. The calculations are illustrated for a simple nonpolar liquid, carbon disulfide, and for liquid water. It is shown that when Onsager's equation is rearranged to a quadratic equation, and a recently found value of the polarizability is employed, its solutions for liquid water yield good agreement with experimental values throughout the whole temperature range. The decrease of the dielectric constant with temperature is essentially linear with the inverse of absolute temperature, but there is additional significant decrease due to the decrease of density with temperature. The relatively high value of the heat of vaporization of liquid water is expressed in terms of large dipolar interaction of a water molecule with the environment, which is due to polarization effects.

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“…Robinson [3] formulated a theory for a single perturber at a fixed inter-nuclear distance with the solute and presented the mechanism by which the forbidden electronic intensity is enhanced by solvent perturbation. Bayliss and Will-Johnson [4] adapted Linder's [5] treatment of dispersion interaction between the solute and solvent by a rapidly oscillating electric field to formulate ''field simulation model''.…”

Section: Introductionmentioning

confidence: 99%

Solvent Perturbation of the Electronic Intensity of Solvated Absorbing Molecules

Ahmed¹,

Obi-Egbedi²,

Iweibo³

2012

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In this paper, we present a general expression originating from quantum-mechanical perturbation treatment of electronic intensities and Hamiltonian operators for the system (H A and H B ) of an absorber and a perturber respectively. The expression is related to the Longuet-Higgins' definition of solute-solvent interaction and fitted into linear regression mode for the determination of transition polarizabilities of 9H-xanthene, 9H-xathone and 9H-xanthione. The result conforms to those earlier obtained when all possible interaction modes are considered.

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Continuum-Model Treatment of Long-Range Intermolecular Forces. I. Pure Substances

Cited by 71 publications

References 11 publications

Dispersion and repulsion contributions to the solvation free energy: Comparison of quantum mechanical and classical approaches in the polarizable continuum model

Dispersion and repulsion contributions to the solvation free energy: Comparison of quantum mechanical and classical approaches in the polarizable continuum model

Continuum reaction field calculation of dielectric constant and vapor pressures for water and carbon disulfide

Solvent Perturbation of the Electronic Intensity of Solvated Absorbing Molecules

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