This book covers the theory and applications of continuum solvation models. The main focus is on the quantum-mechanical version of these models, but classical approaches and combined or hybrid techniques are also discussed. Devoted to solvation models in which reviews of the theory, the computational implementation Solvation continuum models are treated using the different points of view from experts belonging to different research fields Can be read at two levels: one, more introductive, and the other, more detailed (and more technical), on specific physical and numerical aspects involved in each issue and/or application Possible limitations or incompleteness of models is pointed out with, if possible, indications of future developments Four-colour representation of the computational modeling throughout.
Molecular Theory of Solvation presents the recent progress in the statistical mechanics of molecular liquids applied to the most intriguing problems in chemistry today, including chemical reactions, conformational stability of biomolecules, ion hydration, and electrode-solution interface. The continuum model of "solvation" has played a dominant role in describing chemical processes in solution during the last century. This book discards and replaces it completely with molecular theory taking proper account of chemical specificity of solvent. The main machinery employed here is the reference-interaction-site-model (RISM) theory, which is combined with other tools in theoretical chemistry and physics: the ab initio and density functional theories in quantum chemistry, the generalized Langevin theory, and the molecular simulation techniques. This book will be of benefit to graduate students and industrial scientists who are struggling to find a better way of accounting and/or predicting "solvation" properties.
The importance of solvation as a concept which covers quite generally the interactions between a molecular solute particle and a macroscopic body of surrounding solvent is well recognized. Solvation plays a major role in the distribution of elements in the geo- and hydrosphere, and most chemical and biological processes involve solvated reactants and products, the electronic and molecular structure of which are strongly determined by solvation. This three-volume monograph has been written collectively by 50 authors from 14 countries who are specialists in different areas of solvation science. Part A deals with the theory of solvation; Part B is entirely devoted to spectroscopy of solvation; and Part C covers solvation phenomena in specific physical, chemical and biological systems. The volumes will be an invaluable reference source for physicists, physical chemists and biophysicists undertaking investigations into the diversified and fascinating areas of the physics and chemical physics of solvation at postgraduate and professional research levels.
The importance of solvation as a concept which covers quite generally the interactions between a molecular solute particle and a macroscopic body of surrounding solvent is well recognized. Solvation plays a major role in the distribution of elements in the geo- and hydrosphere, and most chemical and biological processes involve solvated reactants and products, the electronic and molecular structure of which are strongly determined by solvation. This three-volume monograph has been written collectively by 50 authors from 14 countries who are specialists in different areas of solvation science. Part A deals with the theory of solvation; Part B is entirely devoted to spectroscopy of solvation; and Part C covers solvation phenomena in specific physical, chemical and biological systems. The volumes will be an invaluable reference source for physicists, physical chemists and biophysicists undertaking investigations into the diversified and fascinating areas of the physics and chemical physics of solvation at postgraduate and professional research levels.
This volume is an interdisciplinary treatise on the theoretical approach to solvation problems. It describes the essential details of the theoretical methods and places them into the context of modern applications, and hence is of broad interest to theoreticians and experimentalists. The assembly of these modern methods and applications into one volume is a unique contribution to date and gives a broad and ample description of the field in its present stage of development.
This book provides a broad and nuanced overview of the achievements and legacy of Professor William (“Bill”) Goddard in the field of computational materials and molecular science. Leading researchers from around the globe discuss Goddard’s work and its lasting impacts, which can be seen in today’s cutting-edge chemistry, materials science, and biology techniques. Each section of the book closes with an outline of the prospects for future developments. In the course of a career spanning more than 50 years, Goddard’s seminal work has led to dramatic advances in a diverse range of science and engineering fields. Presenting scientific essays and reflections by students, postdoctoral associates, collaborators and colleagues, the book describes the contributions of one of the world’s greatest materials and molecular scientists in the context of theory, experimentation, and applications, and examines his legacy in each area, from conceptualization (the first mile) to developments and extensions aimed at applications, and lastly to de novo design (the last mile). Goddard’s passion for science, his insights, and his ability to actively engage with his collaborators in bold initiatives is a model for us all. As he enters his second half-century of scientific research and education, this book inspires future generations of students and researchers to employ and extend these powerful techniques and insights to tackle today’s critical problems in biology, chemistry, and materials. Examples highlighted in the book include new materials for photocatalysts to convert water and CO2 into fuels, novel catalysts for the highly selective and active catalysis of alkanes to valuable organics, simulating the chemistry in film growth to develop two-dimensional functional films, and predicting ligand–protein binding and activation to enable the design of targeted drugs with minimal side effects.
This book deals with a subject that has been studied since the beginning of physical chemistry. Despite the thousands of articles and scores of books devoted to solvation thermodynamics, I feel that some fundamen tal and well-established concepts underlying the traditional approach to this subject are not satisfactory and need revision. The main reason for this need is that solvation thermodynamics has traditionally been treated in the context of classical (macroscopic) ther modynamics alone. However, solvation is inherently a molecular pro cess, dependent upon local rather than macroscopic properties of the system. Therefore, the starting point should be based on statistical mechanical methods. For many years it has been believed that certain thermodynamic quantities, such as the standard free energy (or enthalpy or entropy) of solution, may be used as measures of the corresponding functions of solvation of a given solute in a given solvent. I first challenged this notion in a paper published in 1978 based on analysis at the molecular level. During the past ten years, I have introduced several new quantities which, in my opinion, should replace the conventional measures of solvation thermodynamics. To avoid confusing the new quantities with those referred to conventionally in the literature as standard quantities of solvation, I called these "nonconventional," "generalized," and "local" standard quantities and attempted to point out the advantages of these new quantities over the conventional ones.
This book presents an up-to-date view of theories, practical methods and applications of solvent effects and chemical reactivity in condensed phases. Subjects treated include continuum solvation models, the theoretical basis for the treatment of solvent effects in density functional theory, Monte Carlo simulations of chemical reactions in solution, DFT molecular dynamics simulations, crossing the transition state in solution, valence bond multi-state approach to chemical reactions in solution, quantum theory of solvent effects and chemical reactions. The approaches taken as well as the resulting findings are discussed in detail, thus covering a large part of the methodology currently used in this field. Audience: This volume will be useful to graduate students in chemistry, physical chemistry and biochemistry, to research workers with a background in quantum chemistry and quantum mechanics, to pure and applied quantum chemists, and to industrial molecular modellers.
Ions are ubiquitous in chemical, technological, ecological and biological processes. Characterizing their role in these processes in the first place requires the evaluation of the thermodynamic parameters associated with the solvation of a given ion. However, due to the constraint of electroneutrality, the involvement of surface effects and the ambiguous connection between microscopic and macroscopic descriptions, the determination of single-ion solvation properties via both experimental and theoretical approaches has turned out to be a very difficult and highly controversial problem. This unique book provides an up-to-date, compact and consistent account of the research field of single-ion solvation thermodynamics that has over one hundred years of history and still remains largely unsolved. By reviewing the various approaches employed to date, establishing the relevant connections between single-ion thermodynamics and electrochemistry, resolving conceptual ambiguities, and giving an exhaustive data compilation (in the context of alkali and halide hydration), this book provides a consistent synthesis, in depth understanding and clarification of a large and sometimes very confusing research field. The book is primarily aimed at researchers (professors, postgraduates, graduates, and industrial researchers) concerned with processes involving ionic solvation properties (these are ubiquitous, eg. in physical/organic/analytical chemistry, electrochemistry, biochemistry, pharmacology, geology, and ecology). Because of the concept definitions and data compilations it contains, it is also a useful reference book to have in a university library. Finally, it may be of general interest to anyone wanting to learn more about ions and solvation. Key features: - discusses both experimental and theoretical approaches, and establishes the connection between them - provides both an account of the past research (covering over one hundred years) and a discussion of current directions (in particular on the theoretical side) - involves a comprehensive reference list of over 2000 citations - employs a very consistent notation (including table of symbols and unambiguous definitions of all introduced quantities) - provides a discussion and clarification of ambiguous concepts (ie. concepts that have not been defined clearly, or have been defined differently by different authors, leading to confusion in past literature) - encompasses an exhaustive data compilation (in the restricted context of alkali and halide hydration), along with recommended values (after critical analysis of this literature data) - is illustrated by a number of synoptic colour figures, that will help the reader to grasp the connections between different concepts in one single picture
