On the efficient and accurate short-ranged simulations of uniform polar molecular liquids

Rodgers, Jocelyn M.; Hu, Zhonghan; Weeks, John D.

doi:10.1080/00268976.2011.554332

Cited by 26 publications

(48 citation statements)

References 34 publications

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“…c r w , more accurate than the RPA (16). Although there is progress 3,35 , a systematic and tractable scheme for improving upon the RPA is arguably still missing.…”

Section: Discussionmentioning

confidence: 99%

“…The pair direct correlation function in the mean-field treatment follows from the same treatment that lead to (16). This function depends on λ and is given by:…”

Section: B An Exactly Solvable One-dimensional Modelmentioning

confidence: 99%

“…Moreover, unlike DFT approximations, integral equation theories usually suffer from problems of thermodynamic consistency, important for phase transition studies. A third approach was developed by Weeks, Katsov,Vollmayr and co-workers originally for a LJ fluid [5][6][7][8][9] .More recent extensions of this Local Molecular Field Theory (LMF) have proved remarkably successful in applications to both uniform and non-uniform charged fluids [10][11][12] ,for electrostatics in models of confined water [13][14][15] and for uniform polar molecular liquids 16 .…”

Section: Introductionmentioning

confidence: 99%

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Relationship between local molecular field theory and density functional theory for non-uniform liquids

Archer

Evans

2013

The Journal of Chemical Physics

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The Local Molecular Field Theory (LMF) developed by Weeks and co-workers has proved successful for treating the structure and thermodynamics of a variety of nonuniform liquids. By reformulating LMF in terms of one-body direct correlation functions we recast the theory in the framework of classical Density Functional Theory (DFT). We show that the general LMF equation for the effective reference potential R ( ) φ r follows directly from the standard mean-field DFT treatment of attractive interatomic forces.Using an accurate (Fundamental Measures) DFT for the non-uniform hard-sphere reference fluid we determine R ( ) φ r for a hard-core Yukawa liquid adsorbed at a planar hard wall. In the approach to bulk liquid-gas coexistence we find the effective potentials exhibit rich structure that can include damped oscillations at large distances from the wall as well as the repulsive hump near the wall required to generate the low density 'gas' layer characteristic of complete drying. We argue that it would be difficult to obtain the same level of detail from other (non DFT based) implementations of LMF. LMF emphasizes the importance of making an intelligent division of the interatomic pair potential of the full system into a reference part and a remainder that can be treated in mean-field approximation. We investigate different divisions for an exactly solvable onedimensional model where the pair potential has a hard-core plus a linear attractive tail.Results for the structure factor and the equation of state of the uniform fluid show that including a significant portion of the attraction in the reference system can be much more accurate than treating the full attractive tail in mean-field approximation. We discuss further aspects of the relationship between LMF and DFT.

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“…c r w , more accurate than the RPA (16). Although there is progress 3,35 , a systematic and tractable scheme for improving upon the RPA is arguably still missing.…”

Section: Discussionmentioning

confidence: 99%

“…The pair direct correlation function in the mean-field treatment follows from the same treatment that lead to (16). This function depends on λ and is given by:…”

Section: B An Exactly Solvable One-dimensional Modelmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Relationship between local molecular field theory and density functional theory for non-uniform liquids

Archer

Evans

2013

The Journal of Chemical Physics

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“…This argument matches the results of Rodgers and Weeks [55] in the several instances they considered. Derivations that emphasize alternative (electrostatic) interactions are available elsewhere [56][57][58]. Though the statistical mechanical theory of Eq.…”

Section: Local Molecular Field Theorymentioning

confidence: 99%

Molecular Theory and the Effects of Solute Attractive Forces on Hydrophobic Interactions

et al. 2016

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The role of solute attractive forces on hydrophobic interactions is studied by coordinated development of theory and simulation results for Ar atoms in water. We present a concise derivation of the local molecular field (LMF) theory for the effects of solute attractive forces on hydrophobic interactions, a derivation that clarifies the close relation of LMF theory to the EXP approximation applied to this problem long ago. The simulation results show that change from purely repulsive atomic solute interactions to include realistic attractive interactions diminishes the strength of hydrophobic bonds. For the Ar-Ar rdfs considered pointwise, the numerical results for the effects of solute attractive forces on hydrophobic interactions are of opposite sign and larger in magnitude than predicted by LMF theory. That comparison is discussed from the point of view of quasi-chemical theory, and it is suggested that the first reason for this difference is the incomplete evaluation within LMF theory of the hydration energy of the Ar pair. With a recent suggestion for the system-size extrapolation of the required correlation function integrals, the Ar-Ar rdfs permit evaluation of osmotic second virial coefficients B2. Those B2 also show that incorporation of attractive interactions leads to more positive (repulsive) values. With attractive interactions in play, B2 can change from positive to negative values with increasing temperatures. This is consistent with the historical work of Watanabe, et al., that B2 ≈ 0 for intermediate cases. In all cases here, B2 becomes more attractive with increasing temperature.

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“…We can test the accuracy of this picture by considering various truncated or "short" water models where slowly varying long ranged parts of the Coulomb and LJ interactions in SPC/E water are completely neglected. We first consider a Gaussian-truncated (GT) water model, already studied by LMF theory [28,29,31]. Here the Coulomb potential is separated into short and long ranged parts as v(r) = 1 r = erfc(r/σ)…”

Section: Local Hydrogen Bonds In Full and Truncated Water Potentialsmentioning

confidence: 99%

Deconstructing Classical Water Models at Interfaces and in Bulk

2011

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Using concepts from perturbation and local molecular field theories of liquids we divide the potential of the SPC/E water model into short and long ranged parts. The short ranged parts define a minimal reference network model that captures very well the structure of the local hydrogen bond network in bulk water while ignoring effects of the remaining long ranged interactions. This deconstruction can provide insight into the different roles that the local hydrogen bond network, dispersion forces, and long ranged dipolar interactions play in determining a variety of properties of SPC/E and related classical models of water. Here we focus on the anomalous behavior of the internal pressure and the temperature dependence of the density of bulk water. We further utilize these short ranged models along with local molecular field theory to quantify the influence of these interactions on the structure of hydrophobic interfaces and the crossover from small to large scale hydration behavior. The implications of our findings for theories of hydrophobicity and possible refinements of classical water models are also discussed.

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On the efficient and accurate short-ranged simulations of uniform polar molecular liquids

Cited by 26 publications

References 34 publications

Relationship between local molecular field theory and density functional theory for non-uniform liquids

Relationship between local molecular field theory and density functional theory for non-uniform liquids

Molecular Theory and the Effects of Solute Attractive Forces on Hydrophobic Interactions

Deconstructing Classical Water Models at Interfaces and in Bulk

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