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Author: Paul E. Smith
Publisher: CRC Press
Published: 2016-04-19
Total Pages: 383
ISBN-13: 1439899231
DOWNLOAD EBOOKThere are essentially two theories of solutions that can be considered exact: the McMillan-Mayer theory and Fluctuation Solution Theory (FST). The first is mostly limited to solutes at low concentrations, while FST has no such issue. It is an exact theory that can be applied to any stable solution regardless of the number of components and their co
Author:
Publisher:
Published: 1990
Total Pages: 23
ISBN-13:
DOWNLOAD EBOOKFluctuation Theory develops exact relations between integrals of molecular correlation functions and concentration derivatives of pressure and chemical potential. These quantities can be usefully correlated, particularly for mechanical and thermal properties of pure and mixed dense fluids and for activities of strongly nonideal liquid solutions. The expressions yield unique formulae for the desirable thermodynamic properties of activity and density. The molecular theory origins of the flucuation properties, their behavior for systems of technical interest and some of their successful correlations will be described. Suggestions for fruitful directions will be suggested.
Author: Elizabeth Anne Ploetz
Publisher:
Published: 2014
Total Pages:
ISBN-13:
DOWNLOAD EBOOKThe Kirkwood-Buff (KB) theory of solutions, published in 1951, established a route from integrals over radial (pair) distribution functions (RDFs) in the grand canonical ensemble to a set of thermodynamic quantities in an equivalent closed ensemble. These "KB integrals" (KBIs) can also be expressed in terms of the particle-particle (i.e., concentration or density) fluctuations within grand canonical ensemble regions. Contributions by Ben-Naim in 1977 provided the means to obtain the KBIs if one already knew the set of thermodynamic quantities for the mixture of interest; that is, he provided the inversion procedure. Thus, KB theory provides a two-way bridge between local (microscopic) and global (bulk/thermodynamic) properties. Due to its lack of approximations, its wide ranging applicability, and the absence of a competitive theory for rigorously understanding liquid mixtures, it has been used to understand solution microheterogeneity, solute solubility, cosolvent effects on biomolecules, preferential solvation, etc. Here, after using KB theory to test the accuracy of pair potentials, we present and illustrate two extensions of the theory, resulting in a general Fluctuation Solution Theory (FST). First, we generalize KB theory to include two-way relationships between the grand canonical ensemble's particle-energy and energy-energy fluctuations and additional thermodynamic quantities. This extension allows for non-isothermal conditions to be considered, unlike traditional KB theory. We illustrate these new relationships using analyses of experimental data and molecular dynamics (MD) simulations for pure liquids and binary mixtures. Furthermore, we use it to obtain conformation-specific infinitely dilute partial molar volumes and compressibilities for proteins (other properties will follow) from MD simulations and compare the method to a non-FST method for obtaining the same properties. The second extension of KB theory involves moving beyond doublet particle fluctuations to additionally consider triplet and quadruplet particle fluctuations, which are related to derivatives of the thermodynamic properties involved in regular KB theory. We present these higher order fluctuations obtained from experiment and simulation for pure liquids and binary mixtures. Using the newfound experimental third and fourth cumulants of the distribution of particles in solution, which can be extracted from bulk thermodynamic data using this extension, we also probe particle distributions' non-Gaussian nature.
Author: H. Nomura
Publisher: Elsevier
Published: 1995-12-20
Total Pages: 469
ISBN-13: 0080544770
DOWNLOAD EBOOKThe results of a special research project carried out for "Molecular Approaches to Non-equilibrium Process in Solution" were presented during The 42nd Yamada Conference on "Structure, Fluctuation and Relaxation in Solution" which was held from 11-15 December, 1994. The following topics were discussed at the conference: 1. Solvation Dynamics 2. Relaxation, Fluctuation and Reaction Dynamics 3. Dynamic Structure and Reaction Mechanisms in Solutions. These topics were the main concern of this conference.
Author: Yeqiong Hu
Publisher:
Published: 1997
Total Pages: 354
ISBN-13:
DOWNLOAD EBOOKAuthor: Nikolai B. Melnikov
Publisher: Springer
Published: 2018-08-02
Total Pages: 284
ISBN-13: 3319929747
DOWNLOAD EBOOKThis book presents a theoretical framework for magnetism in ferromagnetic metals and alloys at finite temperatures. The objective of the book is twofold. First, it gives a detailed presentation of the dynamic spin-fluctuation theory that takes into account both local and long-wave spin fluctuations with any frequency. The authors provide a detailed explanation of the fundamental role of quantum spin fluctuations in the mechanism of metallic magnetism and illustrate the theory with concrete examples. The second objective of the book is to give an accurate and self-contained presentation of many-body techniques such as the functional integral method and Green's functions, via a number of worked examples. These computational methods are of great use to solid state physicists working in a range of specialties. The book is intended primarily for researchers, but can also be used as textbook. The introductory chapters offer clear and complete derivations of the fundamentals, which makes the presentation self-contained. The main text is followed by a number of well-organized appendices that contain a detailed presentation of the necessary many-body techniques and computational methods. The book also includes a list of symbols and detailed index. This volume will be of interest to a wide range of physicists interested in magnetism and solid state physics in general, both theoreticians and experimentalists.
Author: Eli Ruckenstein
Publisher: Springer Science & Business Media
Published: 2009-06-17
Total Pages: 349
ISBN-13: 1441904409
DOWNLOAD EBOOKThis book consists of a number of papers regarding the thermodynamics and structure of multicomponent systems that we have published during the last decade. Even though they involve different topics and different systems, they have something in common which can be considered as the “signature” of the present book. First, these papers are concerned with “difficult” or very nonideal systems, i. e. systems with very strong interactions (e. g. , hyd- gen bonding) between components or systems with large differences in the partial molar v- umes of the components (e. g. , the aqueous solutions of proteins), or systems that are far from “normal” conditions (e. g. , critical or near-critical mixtures). Second, the conventional th- modynamic methods are not sufficient for the accurate treatment of these mixtures. Last but not least, these systems are of interest for the pharmaceutical, biomedical, and related ind- tries. In order to meet the thermodynamic challenges involved in these complex mixtures, we employed a variety of traditional methods but also new methods, such as the fluctuation t- ory of Kirkwood and Buff and ab initio quantum mechanical techniques. The Kirkwood-Buff (KB) theory is a rigorous formalism which is free of any of the - proximations usually used in the thermodynamic treatment of multicomponent systems. This theory appears to be very fruitful when applied to the above mentioned “difficult” systems.
Author: Enrique Angel Campanella
Publisher:
Published: 1984
Total Pages: 416
ISBN-13:
DOWNLOAD EBOOKAuthor: Heriberto Cabezas
Publisher:
Published: 1985
Total Pages: 386
ISBN-13:
DOWNLOAD EBOOKFluctuation solution theory relates derivatives of the thermodynamic properties to spatial integrals of the direct correlation functions. This formalism has been used as the basis for a model of aqueous strong electrolyte solutions which gives both volumetric properties and activities. The main thrust of the work has been the construction of a microscopic model for the direct correlation functions. This model contains the correlations due to the hard core repulsion, long range field interactions, and short range forces. The hard core correlations are modeled with a hard sphere expression derived from the Percus-Yevick theory. The long range field correlations are accounted for by using asymptotic potentials of mean force and the hypernetted chain equation. The short range correlations which include hydration and hydrogen bonding are modeled with a density expansion of the direct correlation function. The model requires six parameters for each ion and two for water. The ionic parameters are valid for all solution and those for water are universal. The model has been used to calculate derivative properties for six 1:1 electrolytes in water at 25c, 1 ATM, the calculated properties have been compared to experimentally determined values in order to confirm the adequacy of the model.
Author: John G. Kirkwood
Publisher: CRC Press
Published: 2001-12
Total Pages: 320
ISBN-13: 9780677010304
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