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

Yoshida, Norio

doi:10.5488/cmp.10.3.363

Cited by 11 publications

(8 citation statements)

References 32 publications

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“…65 However, comparisons between RISM theory and molecular Ornstein-Zernike [7][8][9] suggest that approximations to the closure relation, and not orientional averaging, are the principle source of error. 66,67…”

Section: A the Rism And Drism Modelsmentioning

confidence: 99%

Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

Joung

Luchko

Case

2013

The Journal of Chemical Physics

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Using the dielectrically consistent reference interaction site model (DRISM) of molecular solvation, we have calculated structural and thermodynamic information of alkali-halide salts in aqueous solution, as a function of salt concentration. The impact of varying the closure relation used with DRISM is investigated using the partial series expansion of order-n (PSE-n) family of closures, which includes the commonly used hypernetted-chain equation (HNC) and Kovalenko-Hirata closures. Results are compared to explicit molecular dynamics (MD) simulations, using the same force fields, and to experiment. The mean activity coefficients of ions predicted by DRISM agree well with experimental values at concentrations below 0.5 m, especially when using the HNC closure. As individual ion activities (and the corresponding solvation free energies) are not known from experiment, only DRISM and MD results are directly compared and found to have reasonably good agreement. The activity of water directly estimated from DRISM is nearly consistent with values derived from the DRISM ion activities and the Gibbs-Duhem equation, but the changes in the computed pressure as a function of salt concentration dominate these comparisons. Good agreement with experiment is obtained if these pressure changes are ignored. Radial distribution functions of NaCl solution at three concentrations were compared between DRISM and MD simulations. DRISM shows comparable water distribution around the cation, but water structures around the anion deviate from the MD results; this may also be related to the high pressure of the system. Despite some problems, DRISM-PSE-n is an effective tool for investigating thermodynamic properties of simple electrolytes.

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Section: A the Rism And Drism Modelsmentioning

confidence: 99%

Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

Joung

Luchko

Case

2013

The Journal of Chemical Physics

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“…80 Later, the energy gradient technique was also implemented. 81 The 3D-RISM was first combined with the Kohn-Sham density functional theory (KS-DFT). 82 The resulting method was applied to study solvation effects on conformational equilibria, tautomerization energies, and activation barriers 83 through the implementation of the Amsterdam Density Functional (ADF) package with analytical gradients.…”

Section: Rism-scf-sedd: the Second Generationmentioning

confidence: 99%

A modern solvation theory: quantum chemistry and statistical chemistry

Sato

2013

Phys. Chem. Chem. Phys.

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This perspective highlights recent developments in the field of statistical mechanics for molecular liquids, i.e. the integral equation (IE) theory, especially focusing on hybrid approaches incorporating quantum chemistry and IE theory. The electronic structure of solvated molecules is characterized, followed by recent developments and applications. The latter includes for some specific systems: evaluation of acidity, basicity, pH and pKa, chemical equilibrium and molecular structure, chemical reactions, ionization and electron transfer reactions, as well as excited states and their free energy.

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“…Following their study, the combination of the theories has been variously extended both in the electronic structure and integral equation theories. 31,32 Therefore, the RISM theory is also effective in introducing solvent effects into the relativistic electronic structure theory. The DHF/RISM-SCF method presented here, enables the simultaneous description of the detailed solute electronic structure based on the relativistic electronic structure theory and the solvation structure based on molecular theory.…”

Section: Introductionmentioning

confidence: 99%

“…The coupled equations of the Hartree–Fock and RISM equations derived by them are solved self‐consistently, and the electronic wave function of the solute molecule and the solvent distribution can be determined simultaneously. Following their study, the combination of the theories has been variously extended both in the electronic structure and integral equation theories 31,32 . Therefore, the RISM theory is also effective in introducing solvent effects into the relativistic electronic structure theory.…”

Section: Introductionmentioning

confidence: 99%

Solvent effects in four‐component relativistic electronic structure theory based on the reference interaction‐site model

et al. 2022

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A combined method of the Dirac-Hartree-Fock (DHF) method and the reference interaction-site model (RISM) theory is reported; this is the initial implementation of the coupling of the four-component relativistic electronic structure theory and an integral equation theory of molecular liquids. In the method, the DHF and RISM equations are solved self-consistently, and therefore the electronic structure of the solute, including relativistic effects, and the solvation structure are determined simultaneously. The formulation is constructed based on the variational principle with respect to the Helmholtz energy, and analytic free energy gradients are also derived using the variational property. The method is applied to the iodine ion (I À ), methyl iodide (CH 3 I), and hydrogen chalcogenide (H 2 X, where X = O-Po) in aqueous solutions, and the electronic structures of the solutes, as well as the solvation free energies and their component analysis, solvent distributions, and solute-solvent interactions, are discussed.

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

Cited by 11 publications

References 32 publications

Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

Simple electrolyte solutions: Comparison of DRISM and molecular dynamics results for alkali halide solutions

A modern solvation theory: quantum chemistry and statistical chemistry

Solvent effects in four‐component relativistic electronic structure theory based on the reference interaction‐site model

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