Description of a Polar Molecular Liquid in a Disordered Microporous Material With Activating Chemical Groups by a Replica Rism Theory

Hirata,; Kovalenko, V.

doi:10.5488/cmp.4.4.643

Cited by 12 publications

(16 citation statements)

References 56 publications

(191 reference statements)

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“…In the replica RISM approach to the structure and thermodynamics of a quenched-annealed molecular system [49,70,71], the average free energy of molecular fluid (species 1) sorbed in a disordered porous matrix of quenched molecular particles (species 0) is obtained as a statistical average od the fluid free energy at matrix spatial configuration q 0 over the ensemble of matrix realizations,…”

Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

“…The analytic continuation of the RISM integral equations for the annealed (s + 1)-component replicated system to the limit of s → 0 in the assumption of replica symmetry persistence leads to the replica RISM integral equations which yield the radial distribution functions g ij αγ (r) dependent on separation r between interaction sites α and γ of molecular species i, j constituting the quenched-annealed system. Their derivation is given in detail in [70,71]. To provide an adequate description of solution consisting of ions at an arbitrary concentration in polar molecular solvent, Perkyns and Pettitt [76,77] developed the dielectrically consistent RISM theory (DRISM) including a so-called bridge function providing consistency of the solution dielectric properties.…”

Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

“…For simplicity, the temperature of the matrix distribution is assumed to be the same as that of sorbed solution. Different temperatures of the matrix and sorbed fluid lead to new terms in the system thermodynamics [70,71] and can result in non-trivial effects in quenched-annealed systems with charges [60]. The use of such linearized closures as the MSA for the blocking correlations neglects the blocking direct correlation function [62][63][64]67].…”

Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

“…The nanospheres associate into a network of branched chains with fractal dimensionality d ≈ 1.5 persisting up to a length of 100Å and the long-range correlations extending up to 200Å [49]. Previously, we considered a similar fractal structure consisting of interconnected branched chains of associating carbon-like atoms to model microporous carbon material [70,71]. Figure 1 depicts the excess ∆n 00 (r) = n 00 − n (unif) 00 of the running coordination number of nanospheres n 00 (r) over the uniform distribution n (unif) 00 (r) = 4πρ 0 r 3 /3.…”

Section: Modelling Of Nanoporous Carbon Aerogelmentioning

confidence: 99%

“…Recently, we developed a RISM generalization of the replica method to the theory of molecular quenched-annealed systems comprising both fluid and matrix species described with realistic force fields, such as water sorbed in porous carbon aerogel activated with carboxylic groups [70,71]. Along with the distribution functions, we derived closed expressions for the system thermodynamics, in particular the chemical potential and pressure.…”

Section: Introductionmentioning

confidence: 99%

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Molecular Description of Electrolyte Solution in a Carbon Aerogel Electrode

Kovalenko¹,

Hirata²

2003

Condens. Matter Phys.

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We develop a molecular theory of aqueous electrolyte solution sorbed in a nanoporous carbon aerogel electrode, based on the replica reference interaction site model (replica RISM) for realistic molecular quenched-annealed systems. We also briefly review applications of carbon aerogels for supercapacitor and electrochemical separation devices, as well as theoretical and computer modelling of disordered porous materials. The replica RISM integral equation theory yields the microscopic properties of the electrochemical double layer formed at the surface of carbon aerogel nanopores, with due account of chemical specificities of both sorbed electrolyte and carbon aerogel material. The theory allows for spatial disorder of aerogel pores in the range from micro-to macroscopic size scale. We considered ambient aqueous solution of 1 M sodium chloride sorbed in two model nanoporous carbon aerogels with carbon nanoparticles either arranged into branched chains or randomly distributed. The long-range correlations of the carbon aerogel nanostructure substantially affect the properties of the electrochemical double layer formed by the solution sorbed in nanopores.

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Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

Section: Replica Drism-kh-mv Integral Equationsmentioning

confidence: 99%

Section: Modelling Of Nanoporous Carbon Aerogelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Molecular Description of Electrolyte Solution in a Carbon Aerogel Electrode

Kovalenko¹,

Hirata²

2003

Condens. Matter Phys.

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Multiscale Modeling of Solvation

Kovalenko

2017

Springer Handbook of Electrochemical Energy

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Statistical-mechanical, reference interaction site model (RISM) molecular theory of solvation is promising as an essential part of multiscale methodology for chemical and biomolecular nanosystems in solution. Beginning with a force field of site interaction potentials between solution species, it uses a diagrammatic analysis of the solvation free energy to construct integral equations for 3-D spatial correlation functions of molecular interaction sites in the statistical-mechanical ensemble. With the solvation structure so obtained at the level of molecular simulation, 3D-RISM-KH further yields the solvation thermodynamics at once as a simple integral of the correlation functions which is obtained by performing thermodynamic integration analytically. The latter allows analytical differentiation of the free energy functional and thus self-consistent coupling in various multiscale approaches. 3D-RISM-KH has been coupled with the KS-DFT and CASSCF quantum chemistry methods in a self-consistent field description of electronic structure, geometry optimization, nanochemistry, and photochemistry in solution. The multiple time step molecular dynamics of biomolecules steered by effective solvation forces obtained from the 3D-RISM-KH theory, accelerated by the generalized solvation force extrapolation, and stabilized by the optimized isokinetic Nosé-Hoover chain (OIN) thermostat, enables gigantic outer time steps up to tens picoseconds to accurately calculate equilibrium properties.

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