Molecular theory for the phase equilibria and cluster distribution of associating fluids with small bond angles

Marshall, Bennett D.; Chapman, Walter G.

doi:10.1063/1.4816665

Cited by 22 publications

(18 citation statements)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…It is also of interest as a network-forming fluid for its interesting phase behavior and analogies to water and other molecular fluids that form tetrahedral networks. 50,51,57−59 This is the geometry considered throughout the first part of the work presented here.…”

Section: Introductionmentioning

confidence: 99%

Role of Anisotropic Interactions for Proteins and Patchy Nanoparticles

Roberts

Blanco

2014

J. Phys. Chem. B

View full text Add to dashboard Cite

Protein–protein interactions are inherently anisotropic to some degree, with orientation-dependent interactions between repulsive and attractive or complementary regions or “patches” on adjacent proteins. In some cases it has been suggested that such patch–patch interactions dominate the thermodynamics of dilute protein solutions, as captured by the osmotic second virial coefficient (B22), but delineating when this will or will not be the case remains an open question. A series of simplified but exactly solvable models are first used to illustrate that a delicate balance exists between the strength of attractive patch–patch interactions and the patch size, and that repulsive patch–patch interactions contribute significantly to B22 for only those conditions where the repulsions are long-ranged. Finally, B22 is reformulated, without approximations, in terms of the density of states for a given interaction energy and particle–particle distance. Doing so illustrates the inherent balance of entropic and energetic contributions to B22. It highlights that simply having strong patch–patch interactions will only cause anisotropic interactions to dominate B22 solution properties if the unavoidable entropic penalties are overcome, which cannot occur if patches are too small. The results also indicate that the temperature dependence of B22 may be a simple experimental means to assess whether a small number of strongly attractive configurations dominate the dilute solution behavior.

show abstract

Section: Introductionmentioning

confidence: 99%

Role of Anisotropic Interactions for Proteins and Patchy Nanoparticles

Roberts

Blanco

2014

J. Phys. Chem. B

View full text Add to dashboard Cite

show abstract

“…For a sphere to be bonded, it must be in an orientation θ ≤ θc or θ ≥ π -θc. In the absence of an external field these two cases will occur with equal probability yielding the following ODF for bonded spheres (17) U(x) is the Heaviside step function. Note, Eq.…”

Section: Theorymentioning

confidence: 99%

Thermodynamic perturbation theory for associating fluids confined in a one-dimensional pore

Marshall

2015

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

In this paper, a new theory is developed for the self-assembly of associating molecules confined to a single spatial dimension, but allowed to explore all orientation angles. The interplay of the anisotropy of the pair potential and the low dimensional space results in orientationally ordered associated clusters. This local order enhances association due to a decrease in orientational entropy. Unlike bulk 3D fluids which are orientationally homogeneous, association in 1D necessitates the self-consistent calculation of the orientational distribution function. To test the new theory, Monte Carlo simulations are performed and the theory is found to be accurate. It is also shown that the traditional treatment in first order perturbation theory fails to accurately describe this system. The theory developed in this paper may be used as a tool to study hydrogen bonding of molecules in 1D zeolites as well as the hydrogen bonding of molecules in carbon nanotubes.

show abstract

“…Extensions beyond TPT1 have been the topic of much research in recent years. Kalyuzhnyi et al [29][30][31] and Marshall et al developed theory to include multiple bonds per site, [32][33][34][35][36][37] formation of cyclic structures of associated species, [38][39][40] and cooperative hydrogen bonding. 41,42 While the results of these theoretical studies have been confirmed by Monte Carlo simulation (MC), the primary motivation has been in modeling patchy colloids.…”

Section: Introductionmentioning

confidence: 99%

Combination of monovalent and divalent sites on an associating species: Application to water

et al. 2021

Self Cite

View full text Add to dashboard Cite

This contribution is in honor of Professor Keith E. Gubbins, an international leader in developing advances in statistical mechanics and molecular simulation for engineering applications. The research presented here extends the SAFT model that Chapman proposed and developed while a graduate student with Professor Gubbins. In this manuscript, a thermodynamic perturbation theory within a multi-density formalism framework is extended to model species with a combination of monovalent and divalent association sites. Theory predictions are verified with Monte Carlo simulation results for different conditions of temperature, density, and angular size of the divalent site. The theory is applied to model water, where the two lone pairs of electrons on the oxygen atom are represented with a divalent site that includes cooperative hydrogen bonding. The theory results are in good agreement with experiments for saturated densities, vapor pressure, internal energy, and extent of hydrogen bonding.

show abstract

Molecular theory for the phase equilibria and cluster distribution of associating fluids with small bond angles

Cited by 22 publications

References 34 publications

Role of Anisotropic Interactions for Proteins and Patchy Nanoparticles

Role of Anisotropic Interactions for Proteins and Patchy Nanoparticles

Thermodynamic perturbation theory for associating fluids confined in a one-dimensional pore

Combination of monovalent and divalent sites on an associating species: Application to water

Contact Info

Product

Resources

About