The potential distribution theorem and models of molecular solutions / Tom Beck, Michael Paulaitis, Lawrence Pratt.

Format:

Book

Author/Creator:

Beck, Thomas L., 1960-

Contributor:

Paulaitis, Michael E.

Pratt, Lawrence Riley, 1950-

Louis A. Duhring Fund.

Language:

English

Subjects (All):

Molecular theory.

Molecular theory--Problems, exercises, etc.

Genre:

Problems and exercises.

Physical Description:

xiii, 230 pages : illustrations ; 26 cm

Place of Publication:

Cambridge : Cambridge University Press, 2006.

Summary:

An understanding of molecular statistical thermodynamic theory is fundamental to the appreciation of molecular solutions. Though effective monographs on molecular simulation methods are available, down-to-earth presentations of molecular theory are not. This book aims to redress the balance, using the potential distribution theorem (PDT) as the basis, by providing an up-to-date discussion of practical theories in conjunction with simulation results. The authors discuss the field in a concise manner, illustrating the text with useful models of solution thermodynamics and numerous exercises. Modern quasi-chemical theories that permit statistical thermodynamic properties to be studied on the basis of electronic structure calculations are given extended development, as is the testing of those theoretical results with ab initio molecular dynamics simulations. The book is intended for students undertaking research problems of molecular science in chemistry, chemical engineering, biochemistry, pharmaceutical chemistry, nanotechnology, and biotechnology.

Contents:

1.1 Molecules in solution 4

1.2 Looking forward 16

1.3 Notation and the theory of molecular liquids 16

2 Statistical thermodynamic necessities 23

2.1 The free energy and chemical potentials 23

3 Potential distribution theorem 32

3.1 Derivation of the potential distribution theorem 39

3.2 Weak field limit 40

3.3 Potential distribution theorem view of averages 41

3.4 Ensemble dependence 43

3.5 Inhomogeneous systems 44

3.6 Reduced distribution functions 47

3.7 Activity coefficients and solution standard states 51

3.8 Quantum mechanical ingredients and generalizations 53

4 Models 61

4.1 Van der Waals model of dense liquids 61

4.2 Dielectric solvation - Born - models 67

4.3 Excluded volume interactions and packing in liquids 73

4.4 Flory-Huggins model of polymer mixtures 78

4.5 Electrolyte solutions and the Debye-Huckel theory 89

4.6 Clustering in dilute solutions and Pitzer models 94

5.1 Reference systems and umbrella sampling 100

5.2 Overlap methods 104

5.3 Perturbation theory 105

5.4 Thermodynamic integration 116

5.5 Bias 118

5.6 Stratification 120

6 Statistical tentacles 123

6.1 The MM and KS expansions 123

6.2 Density functional and classic integral equation theories 132

6.3 Kirkwood-Buff theory 140

7 Quasi-chemical theory 142

7.1 Derivation of the basic quasi-chemical formula 143

7.2 Clustering in more detail 146

7.3 An example of a primitive quasi-chemical treatment: Be[superscript 2+](aq) 149

7.4 Analysis of ab initio molecular dynamics 153

7.5 Packing in classical liquids 157

7.6 Self-consistent molecular field for packing 160

7.7 Historical quasi-chemical calculation 166

7.8 Explicit-implicit solvent models 168

8 Developed examples 172

8.1 Polymers 172

8.2 Primitive hydrophobic effects 180

8.3 Primitive hydrophilic phenomena: ion hydration 198.

Notes:

Includes bibliographical references and index.

Local Notes:

Acquired for the Penn Libraries with assistance from the Louis A. Duhring Fund.

ISBN:

9780521822152

0521822157

051124049X

9780511240492

0511241011

9780511241017

OCLC:

60794227

Online:

Publisher description

Contributor biographical information