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by Sture Nordholm, Jan Forsman, and Cliff Woodward

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380 pages9 hours

*Generalized van der Waals Theory of Molecular Fluids in Bulk and at Surfaces* presents successful research on the development of a new density theory of fluids that makes it possible to understand and predict a wide range of properties and phenomena. The book brings together recent advances relating to the Generalized van der Waals Theory and its use in fluid property calculations. The mathematics presentation is oriented to an audience of varying backgrounds, and readers will find exercises that can be used as a textbook for a course at the upper undergraduate or graduate level in physics or chemistry.

In addition, it is ideal for scientists from other areas, such as geophysics, oceanography and molecular biology who are interested in learning about, and understanding, molecular fluids.

Presents an approximate, but fully derived and physically explained, theory of molecular fluids to facilitate broad applications Derives a density functional theory of classical fluids and applies it to obtain equations of state, as well as non-uniform fluid properties, e.g., surface tension and adsorption Demonstrates how the theory can be applied to complex multi-center molecules forming a polymer fluid Provides user-friendly programs to redraw figures for variable parameters and to perform calculations in particular applications Includes a set of exercises to support use of the book in a coursePublisher: Elsevier ScienceReleased: Sep 5, 2018ISBN: 9780128111901Format: book

surfaces

This book is, in spirit and essence, a manual to a modern version of the approach to molecular fluids pioneered by van der Waals some 150 years ago. The generalized van der Waals

(GvdW) theory described here was developed over the last 40 years. This modern version of the theory has appropriated the mathematical structure of a density functional theory

(DFT), characterized by the use of single molecule densities to express the free energy which is minimized to obtain the response of a fluid to imposed boundary conditions and applied external potentials. The primary intention of this book is to both present the theory in a transparent way and show how it can be applied to a wide range of types of fluids and conditions. It is our hope that the reader will readily see how the theory was used in the various problems that we cover, and further appreciate how it can be used in other applications. Simplicity and generality have guided us not only in our exposition, physical analysis and interpretations but also in the mathematical implementation of the theory.

The motivation for writing the book at this point is that the GvdW theory, which was initially far from mainstream fluid theory, has now amply proven its ability to resolve an impressive range of fluid properties by relatively simple analysis and efficient calculation. Hence it seems the time is right to present a more complete picture of the theory and its performance in a range of fundamental applications, both traditional and modern in nature. The GvdW theory is based on some strong assumptions and has used a wide variety of approximations to realize its goals. Critical appraisal is needed, but we take the attitude that assumptions and approximations are a valuable, and often essential, part of theory if they are (i) fully known to the user; (ii) physically justified and (iii) capable of delivering useful accuracy in efficient calculations. While we have, of course, sought to obtain good accuracy with the theory, there is some advantage to trading some accuracy for both physical insight and ease of calculation. From this perspective the GvdW theory is well served by accompanying numerical simulations using either molecular dynamics (MD) or Monte Carlo (MC). While simulations provide a flexible approach and highly accurate predictions of physical models for molecular fluids, they are essentially brute force numerical experiments

performed in simulations which require a lot of computational resources while not always providing physical explanation and understanding. On the other hand, we believe that one could hope to obtain both accuracy and physical understanding by the use of GvdW theory and MD or MC simulations on the same systems. Moreover, verified accuracy of the GvdW theory may provide systematic results by quick calculation and, in some cases, allow larger systems to be studied than possible by simulations.

Our clear focus on the GvdW theory will hopefully improve the readability and the insight gained by the reader, but there are also some corresponding limitations associated with the chosen format of our book. A manual of GvdW theory is not a review of either molecular fluid properties and phenomena or of the many types of theory used to resolve them. Naturally, the development of the GvdW theory has been done in the light of alternative theories available in the literature. We provide a list of books that summarize the background of alternative theory against which our work can be seen, but we will not review relationships between GvdW and other theories in the detailed developments or applications. The fact is that most of the developments are original and relate more to the distant field of density functional theory of electronic structure than to alternative fluid theory. Certainly, the following derivations and applications often rely on comparison with numerical simulations by the Monte Carlo method. We assume that the reader is aware of this method as a numerical experiment performed on the chosen molecular fluid model within the constraints of (i) classical mechanics and (ii) a system which is either finite in particle number or infinite but constrained by periodic boundary conditions.

Our natural wish as authors is for a readership drawn from a population of broad scope, but obviously the format, level and content of the book needs to have a focal point somewhere in the desired range of readership. The origin of the book has been a set of lecture notes accompanying a course on Statistical Thermodynamics given at the University of Gothenburg mostly for beginning graduate students in chemistry or physics from both the host and other universities in Sweden. This identifies the focal point among intended readers of the book. The aim has been to place the theoretical tools in the hands of these graduate students to take up the study of molecular fluids by density functional theory derived from the original ideas of van der Waals. This should not be a forlorn hope. Two of the authors have entered this book project through the attendance of the underlying course. Advanced undergraduate students have successfully attended this course as well over the years but probably found it taxing. Naturally we hope to attract other readers and users among fellow researchers in molecular fluid theory. The GvdW theory is, we believe, best used together with other theories. The particular advantage of the combination of numerical simulation and GvdW theory has been mentioned already but other combinations are also fruitful, e.g., with pair-correlation theories or lattice theories. Each has its underlying approximations, and seeing how different theories fare against simulation or experiment tells us about the validity of corresponding approximations.

Finally, we wish to express a hope that our book will be read by many who do not normally work with fundamental theory. A great advantage of the original van der Waals theory was, and still is, its persuasive physical nature and little need for a mathematical edifice that could hide its logic and dissuade some from using it. The extensions introduced here to make the GvdW theory measure up to modern expectations, e.g., the format of a density functional theory, necessarily introduces some additional mathematics but it is not excessive. We believe most of the simplicity of van der Waals theory is still intact in GvdW theory. We therefore hope to find readers among experimentalists, engineers and others not normally concerned with fluid theory. In fact, this hope is an important motivation for the writing of this book.

Books on Statistical Mechanics which provide a good background for this book can be found listed below **[1–20]. The published record for the GvdW theory can be found below as well [21–73]. **

[1] D.J. McQuarrie, J.D. Simon, *Molecular Thermodynamics*. University Science Books; 1999.

[2] K.S. Pitzer, *Thermodynamics*. 3rd edition McGraw–Hill International Editions; 1995.

[3] G.C. Maitland, M. Rigby, E.B. Smith, W.A. Wakeham, *Intermolecular Forces – Their Origin and Determination*. Oxford Science Publications; 1981.

[4] T. Hill, *An Introduction to Statistical Thermodynamics*. Addison–Wesley Publishing Company, Inc.; 1960.

[5] D.F. Evans, H. Wennerström, *The Colloidal Domain – Where Physics, Chemistry, Biology and Technology Meet*. VCH Publishers, Inc.; 1994.

[6] P.A. Egelstaff, *An Introduction to the Liquid State*. Academic Press; 1967.

[7] A.J. Stone, *The Theory of Intermolecular Forces*. Oxford: Clarendon Press; 1996.

[8] J.N. Israelachvili, *Intermolecular and Surface Forces – with Applications to Colloidal and Biological Systems*. Academic Press;

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