Free energy functions in the extended RISM approximation

Singer, Sherwin J.; Chandler, David

doi:10.1080/00268978500101591

Cited by 344 publications

(273 citation statements)

References 5 publications

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“…The distribution functions predicted by the IEs can be used to describe much of the thermodynamics of the solution mixture but remain inherently approximate. Statistical thermodynamics provides convenient analytical expressions for the solution thermodynamics using the site-site distribution functions 43,44 . Some recent advances in IE theory offer more rigor and accuracy but have yet to be extended to aqueous systems 41 .…”

Section: Introductionmentioning

confidence: 99%

Integral Equation Study of the Hydrophobic Interaction between Graphene Plates

Howard

Perkyns

Choudhury

et al. 2008

J. Chem. Theory Comput.

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The hydrophobic association of two parallel graphene sheets is studied using the 3D-RISM HNC integral equations with several theoretical methods for the solvent distribution functions. The potential of mean force is calculated to study the effects of the aqueous solvent models and methods on the plates as a function of distance. The results of several integral equations (IE) are compared to MD simulations for the same model. The 3D-IEs are able to qualitatively reproduce the nature of the solvent effects on the potential of mean force but not quantitatively. The local minima in the potential of mean force occur at distances allowing well defined layers of solvent between the plates but are not coincident with those found in simulation of the same potential regardless of the theoretical methods tested here. The dewetting or drying transition between the plates is generally incorrectly dependent on steric effects with these methods even for very hydrophobic systems without solutesolvent attractions, in contradiction with simulation.

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Section: Introductionmentioning

confidence: 99%

Integral Equation Study of the Hydrophobic Interaction between Graphene Plates

Howard

Perkyns

Choudhury

et al. 2008

J. Chem. Theory Comput.

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“…Within the context of the extended RISM theory in conjunction with the HNC analogue closure equation, Singer and Chandler 45 have shown that the solvation free energy of a solute molecule at infinite dilution can be written in an analytical form and without integration over a coupling parameter . This solvation free energy expression is 46…”

Section: ͑7͒mentioning

confidence: 99%

“…Details of the theory are described in the literature. 9,10,45,46 Essentially, the RISM equation 11 is an Ornstein-Zernike-like relation between the site-site pair correlation functions h i j and the direct correlation functions…”

Section: B the Extended Rism Equationmentioning

confidence: 99%

Solvent-induced interactions between hydrophobic and hydrophilic polyatomic sheets in water and hypothetical nonpolar water

Koga

Zeng

Tanaka

1997

The Journal of Chemical Physics

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"Solvent-induced interactions between hydrophobic and hydrophilic polyatomic sheets in water and hypothetical nonpolar water" (1997 Hydrophobic and hydrophilic interactions are two major intermolecular forces between hydrophobic nonpolar and hydrophilic polar sites of macromolecules or materials surfaces in solvents. To further understand these two interactions at the microscopic level, an idealized polyatomic model is devised, which includes hydrophobic, hydrophilic, and partially hydrophilic polyatomic planar square molecular sheets. The hydrophobic molecular sheet is composed of the Lennard-Jones particles while the hydrophilic molecular sheet consists of positive and negative charge sites. In the framework of the extended reference interaction site model integral equation theory the solvent-induced interactions ͑or the potential of mean forces͒ between two parallel molecular sheets in water and in the hypothetical nonpolar water are investigated in a systematic fashion. Such a highly idealized model allows us to isolate and to explore the important effects of molecular size, relative intermolecular position ͑e.g., in-or out-of-registry configuration͒, and hydrophilic site distribution on the hydrophobic and hydrophilic interactions in both water and the hypothetical nonpolar water. Significant insight into these effects at the molecular level is obtained. For the hydrophobic planar molecules in water we find solvent separated hydrophobic interaction becomes less favored as sheet size increases. Moreover, the contact hydrophobic interaction between two molecular sheets in the out-of-registry configuration is always most favorable. For the latter case we find it is the van der Waals attraction, rather than the hydrophobic attraction, that dominates the total interaction. We also find that in both water and the hypothetical nonpolar water the solvent-induced interaction between two hydrophobic sheets behaves similarly. One possible explanation is that the hydrophobic hydration originating from the hydrogen bonding network in water plays an insignificant role in the solvent-induced interaction, at least in the infinitely dilute aqueous solution. For hydrophilic planar molecular sheets in water, we find water-induced hydrophilic interaction is much more substantial compared with the hydrophobic one. In many cases, the hydrophilic interaction is found directly against the intermolecular force between two parallel molecular sheets in vacuum. Finally, for the partially hydrophilic planar molecules in water, a newly discovered feature is that a disperse hydrophilic site distribution gives rise to stronger solvent-induced interaction compared with the clustered hydrophilic site distribution.

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“…Here H 0 is Fock operator in gas phase, ψ is the wave function of solute, and ∆µ is the excess chemical potential which is the functional of the solute-solvent total correlation function h(ω 1 ω 2 R 12 ) and the direct correlation function c(ω 1 ω 2 R 12 ) as well as the solute-solvent interaction energy u(ω 1 ω 2 R 12 ) [14];…”

Section: Moz-scf Formalismmentioning

confidence: 99%

“…An analytical expression of the free energy gradients in the RISM-SCF formalism was proposed by Sato et al [12,13]. They have reformulated the RISM-SCF equations with the use of the free-energy expression introduced by Singer and Chandler [14]. It has been shown that the derivation automatically provides variational conditions for multiconfigurational self-consistent-field (MCSCF) wave functions as well as the Hartree-Fock (HF) wave functions.…”

Section: Introductionmentioning

confidence: 99%

Analytical free energy gradient for the molecular Ornstein-Zernike self-consistent-field method

Yoshida¹

2007

Condens. Matter Phys.

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An analytical free energy gradient for the molecular Ornstein-Zernike self-consistent-field (MOZ-SCF) method is presented. MOZ-SCF theory is one of the theories to considering the solvent effects on the solute electronic structure in solution. [Yoshida N. et al., J. Chem. Phys., 2000, 113, 4974] Molecular geometries of water, formaldehyde, acetonitrile and acetone in water are optimized by analytical energy gradient formula. The results are compared with those from the polarizable continuum model (PCM), the reference interaction site model (RISM)-SCF and the three dimensional (3D) RISM-SCF.

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Free energy functions in the extended RISM approximation

Cited by 344 publications

References 5 publications

Integral Equation Study of the Hydrophobic Interaction between Graphene Plates

Integral Equation Study of the Hydrophobic Interaction between Graphene Plates

Solvent-induced interactions between hydrophobic and hydrophilic polyatomic sheets in water and hypothetical nonpolar water

Analytical free energy gradient for the molecular Ornstein-Zernike self-consistent-field method

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