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We develop the first comprehensive approach to model associating fluids with small bond angles using Wertheim's perturbation theory. We show theoretically and through monte carlo simulations that as bond angle is varied various modes of…

Soft Condensed Matter · Physics 2013-08-27 B. D. Marshall , W. G. Chapman

It has been extensively demonstrated through first principles quantum mechanics calculations that water exhibits strong hydrogen bond cooperativity. Classical molecular simulation and statistical mechanics methods typically assume pairwise…

Soft Condensed Matter · Physics 2017-05-24 Bennett D. Marshall

An alternative way of utilizing the thermodynamic perturbation theory of Wertheim for the development of equations of state for associating fluid models is presented and detailed for water. The approach makes use of general features of the…

Soft Condensed Matter · Physics 2021-10-12 I. Nezbeda

We develop a resummed thermodynamic perturbation theory for bond cooperativity in associating fluids by extension of Wertheim's multi - density formalism. We specifically consider the case of an associating hard sphere with two association…

Soft Condensed Matter · Physics 2013-12-19 B. D. Marshall , W. G. Chapman

In this work we develop a new classical perturbation theory for water which incorporates the transition to tetrahedral symmetry in both the dispersion and hydrogen bonding contributions to the free energy. This transition is calculated…

Soft Condensed Matter · Physics 2019-03-25 Bennett D. Marshall

In this paper we develop a thermodynamic perturbation theory for two site associating fluids which exhibit bond cooperativity. We include both steric hindrance and ring formation such that the equation of state is bond angle dependent. Here…

Soft Condensed Matter · Physics 2015-06-19 B. D. Marshall , Amin Haghmoradi , W. G. Chapman

Thermodynamic properties of the particles interacting through smooth version of Stell-Hemmer interaction were studied using Wertheim's thermodynamic perturbation theory. The temperature dependence of molar volume, heat capacity, isothermal…

Soft Condensed Matter · Physics 2013-12-18 T. Urbic

We critically discuss the application of the Wertheim's theory to classes of complex associating fluids that can be today engineered in the laboratory as patchy colloids and to the prediction of their peculiar gas-liquid phase diagrams. Our…

Soft Condensed Matter · Physics 2016-01-06 Riccardo Fantoni , Giorgio Pastore

This document outlines the development of numerous new theoretical approaches to model associating fluids. For a detailed abstract please see page ii.

Soft Condensed Matter · Physics 2014-05-09 B. D. Marshall

We extend Wertheim's thermodynamic perturbation theory to derive the association free energy of a multicomponent mixture for which double bonds can form between any two pairs of the molecules' arbitrary number of bonding sites. This…

Soft Condensed Matter · Physics 2021-02-26 Michael P. Howard , Zachary M. Sherman , Delia J. Milliron , Thomas M. Truskett

We show that the formalism of Wertheim's first order thermodynamic perturbation theory can be generalised for the fluid of rotating sticky particles with anisotropic hard core confined to a quasi-one-dimensional channel. Using the transfer…

Statistical Mechanics · Physics 2025-10-09 Péter Gurin , Szabolcs Varga

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…

Soft Condensed Matter · Physics 2016-04-27 Bennett D. Marshall

We consider instability of the Friedmann world model to the second-order in perturbations. We present the perturbed set of equations up to the second-order in the Friedmann background world model with general spatial curvature and the…

Astrophysics · Physics 2009-11-07 H. Noh , J. Hwang

The theoretical description of the thermodynamics of water is challenged by the structural transition towards tetrahedral symmetry at ambient conditions. As perturbation theories typically assume a spherically symmetric reference fluid,…

Soft Condensed Matter · Physics 2017-11-15 Bennett D. Marshall

In this paper we develop the first equation of state for alcohol containing mixtures which includes the effect of steric hindrance between the two electron lone pair hydrogen bond acceptor sites on the alcohol's hydroxyl oxygen. The theory…

Soft Condensed Matter · Physics 2018-10-02 Bennett D. Marshall

Compressing or cooling a fluid typically enhances its static interparticle correlations. However, there are notable exceptions. Isothermal compression can reduce the translational order of fluids that exhibit anomalous waterlike trends in…

Soft Condensed Matter · Physics 2008-04-11 William P. Krekelberg , Jeetain Mittal , Venkat Ganesan , Thomas M. Truskett

The first well founded perturbation theory for classical solid systems is presented. Theoretical approaches to thermodynamic and structural properties of the hard-sphere solid provide us with the reference system. The traditional…

Condensed Matter · Physics 2009-10-28 C. Rascon , L. Mederos , G. Navascues

First steps towards developing a new perturbation theory for molecular liquids are taken. By choosing a new form of splitting the site-site potential functions between molecules, we will get a set of atomic fluids as the reference system…

Chemical Physics · Physics 2017-11-21 Mehrdad Khanpour

Two theories for associating fluids recently used to study clustering in models for self-assembling patchy particles, Wertheim's and Bjerrum-Tani-Henderson theories, are carefully compared. We show that, for a fluid allowing only for…

Statistical Mechanics · Physics 2014-08-26 Riccardo Fantoni , Giorgio Pastore

In this work we extend Wertheim's thermodynamic perturbation theory (TPT) to binary mixtures (species A and species B) of patchy colloids where each species has a single patch which can bond a maximum of twice (divalent). Colloids are…

Soft Condensed Matter · Physics 2014-08-16 B. D. Marshall , W. G. Chapman
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