Electronic Structure and Properties of Transition Metal Compounds E-Book

Isaac B. Bersuker

• Herausgeber: John Wiley & Sons
• Kategorie: Wissenschaft und neue Technologien
• Sprache: Englisch

Seitenzahl: 1527

Veröffentlichungsjahr: 2025

Beschreibung

Presents the latest achievements in the theory of electronic structure and properties of transition metal coordination compounds with applications to a range of chemical and physical problems

Electronic Structure and Properties of Transition Metal Compounds offers a detailed and authoritative account of the theory of electronic structure and the properties of transition metal compounds with applications to various chemical and physical problems.

The fully updated third edition incorporates recent developments and methods in the field, including new coverage of methods of ab initio calculations of the electronic structure of coordination compounds and the application of vibronic coupling and the Jahn-Teller effect to solve coordination chemistry problems. Revised chapters provide up-to-date views on reactivity, chemical activation, and catalysis. New and expanded questions, exercises, and problems in each chapter are supported by new problem-solving examples, illustrations, graphic presentations, and references.

Designed to be intelligible to advanced students, researchers, and instructors, Electronic Structure and Properties of Transition Metal Compounds:

• Provides thorough coverage of the theory underlying the electronic structure and properties of transition metal compounds, including the physical methods of their investigation
• Helps readers understand the origin of observable properties in transition metal compounds and choose a suitable method of their investigation
• Contains numerous problems with solutions and illustrative examples demonstrating the application of the theory to solving specific chemical and physical problems
• Presents a generalized view of the modern state of the field, beginning from the main ideas of quantum chemistry and atomic states to applications to various chemical and physical problems
• Features novel problems never fully considered in books on coordination chemistry, such as relativistic effects in bonding, optical band shapes, and electron transfer in mixed-valence compounds

Electronic Structure and Properties of Transition Metal Compounds: Theory and Applications, Third Edition is an excellent textbook for graduate and advanced undergraduate chemistry students, as well as a useful reference for inorganic, bioinorganic, coordination, organometallic, and physical chemists and industrial and academic researchers working in catalysis, organic synthesis, materials science, and physical methods of investigation.

Leseprobe

Electronic Structure and Properties of Transition Metal Compounds

Theory and Applications

Third Edition

Isaac B. Bersuker

The University of Texas at Austin

USA

Yang Liu

Harbin Institute of Technology

China

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Library of Congress Cataloging-in-Publication DataNames: Bersuker, I. B. (Isaac Borisovich), author.Title: Electronic structure and properties of transition metal compounds : theory and applications / Isaac B. Bersuker, the University of Texas at Austin, USA, Yang Liu, Harbin Institute of Technology, China.Description: Third edition. | Hoboken, NJ : Wiley, [2025] | Includes bibliographical references and index.Identifiers: LCCN 2024033106 (print) | LCCN 2024033107 (ebook) | ISBN 9781394178896 (hardback) | ISBN 9781394178902 (adobe pdf) | ISBN 9781394178919 (epub)Subjects: LCSH: Transition metal compounds.Classification: LCC QD172.T6 B48 2025 (print) | LCC QD172.T6 (ebook) | DDC 546/.6–dc23/eng20241010LC record available at https://lccn.loc.gov/2024033106LC ebook record available at https://lccn.loc.gov/2024033107

Cover Design: WileyCover Image: Courtesy of Yang Liu

Preface to the Third Edition

In the present, third edition of this book, as compared to the previous two editions [1, 2], significant changes are related, first of all, to the attempt to take into account the latest achievements in this field in both the theory and applications, and to add more illustrative examples, along with other minor corrections. Significant additions and improvements are introduced in all the 11 chapters, especially in Chapters 3, 5, 6, 7, and 11, and in questions, problems, appendixes, and references, as well as in the resolution of most figures. On a more fundamental view, the new edition explores in much more details the role of the nuclear framework and the electron–nuclear (vibronic) interactions in the formation of space configurations of polyatomic systems and their transformations, directly related to the observable properties, including chemical reactions. More introductory information for the reader is presented below in the Prefaces to, respectively, the second and the first editions of this book, as well as in the Foreword to the first edition, written by the classics of coordination chemistry A. Cotton and J. Fackler [1]. But much more detailed information about the role and scope of the book is given in its special Chapter 1, titled “Subject and Methods.”

As a very brief summary, the main objectives of this book are to reveal a general and most modern view on the theory of electronic structure and properties of transition metal compounds with applications to various chemical and physical problems, presented in a way intelligible to students, researchers, and teachers, and usable also as a textbook for graduate and advanced undergraduate students.

Some comments are worthwhile about the meaning of the notion “Introduction to the Theory” given as a subtitle to the title of the first two editions of this book [1, 2] and changed to “Theory and Applications” in the present third edition. The “Introduction to the Theory” notice was meant to emphasize that the book is addressed also to those who have not studied any special theory of electronic structure of transition metal coordination compounds (but who have some background in quantum theory in the volume of a regular course for chemists). It also implied that the book is not devoted to the advances of the theory itself, its sophisticated formulations and methodologies. Instead, the latest achievements of the theory were presented together with explanations of how they have been obtained (but without bulky mathematical deductions) and how they can be used to solve physical and chemical problems. Further developments of the theory itself form a part of quantum chemistry, well presented in the literature. With the extensions and additions to this volume, and following many notices of the readers, the subtitle “Theory and Applications” seems to be more appropriate to this third edition.

In view of the increased volume of information in this field and to reduce the time for preparation of this edition, Dr. Yang Liu from Harbin Institute of Technology, China, a high‐level expert in this field, agreed to coauthor this third edition of the book, for what Dr. Bersuker is very thankful.

Isaac B. Bersuker

Yang Liu

May, 2024

References

1

I. B. Bersuker,

Electronic Structure and Properties of Transition Metal Compounds. Introduction to the Theory

, Wiley, New York, 1996.

2

I. B. Bersuker,

Electronic Structure and Properties of Transition Metal Compounds. Introduction to the Theory

, 2nd ed., Wiley, New York, 2010.

Extract from the Preface to the Second Edition

In rewriting the first edition of this book, two goals were pursued. The first one is educational, to make the book more accessible to graduate and advanced undergraduate students and to supplement the presentation with additional “infrastructure” that allows the reader to use the book as a textbook for special courses. The second goal, although more usual, is no less important; it strives from the necessity to renew the material of the book in view of the fast development of this field during the last two decades.

For the educational goal the narrative is given in maximum possible plain language accompanied by many boxed “Examples” showing explicitly how the theory is applied to solving specific chemical problems, and each chapter is supplemented by “Summary Notes,” “Questions,” “Exercises,” and “Problems.” These supplements serve as a guide to learning and adoption of the subject by the students, and to help the instructor of the course. Some of these additions are on the level of chemical problem‐solving with detailed solutions given at the end of the book.

Beside these essential educational improvements, the book preserves and enhances the first edition’s role as a source of information on the basics of electronic structure and properties of transition metal systems (TMSs) in its most modern understanding, and with emphasis on origins and physical meaning. All the chapters are corrected and updated, but essential changes were introduced in Chapters 5–9, especially in Chapters 5 and 8. In particular, in Chapter 5 combined quantum–classical (QM/MM) methods of modeling large organometallic systems are described and examples of QM/MM calculations for specific TMS are given. In the same chapter, an extended presentation of the density‐functional methods of electronic structure calculations (which have reached widespread use also by non‐experts) is given together with examples of computations using free programs downloaded from the Internet. Similar examples are also given for semiempirical and ab initio methods of computation. In Chapter 8 some important physical methods of investigation are added, including a section on gamma‐resonance spectroscopy, as well as further description of IR, Raman, and charge transfer spectra.

The special boxed “Examples” in nine chapters of the book (a total of 70) supplement the theoretical methods and results, making them more accessible and understandable. They may serve also as separate essays—solutions of chemical problems by means of theoretical methods, and therefore they are indicated on a separate line in the book Contents.

The role and place of this book among others available is outlined in the introductory Chapter 1, but I should like to note here the (unique of this kind) attempt to promote a novel, more general agenda (with a higher level of theory and understanding) of the role of electronic structure in formation and transformation of matter. With regard to TMS, the first significant level of electronic theory was reached in the 1950s–1960s by crystal field theory. A higher level of theory was achieved in the 1980s–1990s, based on computer developments that allowed for full molecular orbital and density‐functional electronic structure calculations.

However, in the last two to three decades a new, higher level of understanding of the role of electronic structure in properties of matter emerged that has not yet been assimilated by the lay chemist and physicist, and still has not been introduced in teaching of this subject. The novel understanding is related to the ways in which the electrons control molecular transformation. It turns out that nuclear configuration changes are dependent on the electronic structure that essentially involves excited electronic states. The point is that quantum separation of ground and excited electronic states is valid only for given, fixed positions of the nuclei; any displacement of the latter mixes the initial ground and excited or degenerate states, and this mixing is crucial in understanding the origin of nuclear configuration changes. Mixing electronic states, ground and excited, degenerate and nondegenerate, solely determines all possible nuclear configuration instabilities, distortions, and transformations, including formation of molecular shapes and crystal lattices, conformational changes and phase transitions, chemical activation, and mechanism of chemical reactions, to mention a few.

Comprehending this nuclear‐dynamical aspect of electronic structure elevates the theory to a new, higher level and facilitates a better understanding of chemical and physical phenomena. The intention of this book is to instill this advanced way of thinking in physics and chemistry. It is given in many parts of the book as a paradigm, more noticeable and explicitly in Section 7.4 with applications in subsequent chapters, especially Chapters 9–11.

In preparation of this book, I benefited from the help of my students and colleagues, many of whom were mentioned in the Preface to the first edition. For the present (second) edition, I received further assistance from J. E. Boggs, P. Garcia‐Fernandez, V. Z. Polinger, B. S. Tsukerblat, M. D. Kaplan, S. A. Borshch, S. S. Stavrov, G. I. Bersuker, L. F. Chibotaru, I. Ya. Ogurtsov, N. N. Gorinchoy, Wenli Zou, and Yang Liu. I am grateful also to F. A. Cotton and J. P. Fackler, Jr., for their foreword to the first edition. Special thanks are due to Professor Charles Dismukes (Princeton University), who used the first edition as a textbook to his courses and provided us with a variety of comments and questions, as well as corrections to misprints and omissions.

Isaac B. Bersuker

Austin, Texas, March 2009

Extracts from the Preface to the First Edition

Presently transition metal compounds form a number of research fields with vast applications ranging from a variety of magnetic, ferroelectric, and superconducting materials to all kinds of catalysts, to metallobiochemical systems of vital importance. The main goal of this book is to provide a comprehensive discussion of the latest developments in the study of electronic structure and related properties of transition metal coordination systems, and to present the subject in a form suitable for chemists and physicists—students, researchers, and teachers.

Most attention is paid to a better understanding of the basic principles, general features, and specifics of electronic properties affecting ligand bonding, stereochemistry and crystal chemistry, chemical reactivity, electron transfer and redox phenomena, as well as spectroscopic, magnetic, and electronic density distribution properties. The discussion of relativistic effects in bonding, presented in a book context for the first time, elucidates the origin of important properties including, for instance, the “nobleness” and the yellow color of gold.

Quite novel are the implications of vibronic effects in chemical and physical phenomena presented in this book. The concept of vibronic interactions developed during the last two decades as a perturbational approach to the coupling between the electronic motion and nuclear configuration contributes significantly to the solution of a number of problems. These include, for instance, band shapes of electronic and photoelectron spectra, local stereochemistry and structural phase transitions in crystals, plasticity, distortion isomers, and temperature dependent conformers, molecular pseudorotations, chemical activation by coordination, and electron‐conformational effects in biological systems.

One of the special features of this book is that it includes both the theory of electronic structure and its applications to various problems. Significant efforts were made to present the whole topic in a unified fashion with indications of direct and indirect links between its numerous more specific aspects and to make the presentation understandable without oversimplification. Many examples are provided, which will assist the reader in understanding how theoretical concepts can be applied to laboratory problems.

During the preparation of this book, I benefited from the help and cooperation of my students and co‐workers, as well as from suggestions of many colleagues throughout the world. I am very grateful to all of them.

Isaac B. Bersuker

Austin, Texas, April 1995

Foreword to the First Edition

While several major treatises have been published in the English language that purport to cover the topic of this volume, none has appeared in more than a decade. Advances in computing during this time have put the tools of the theoretical chemist in the hands of the experimentalist. The use of these tools requires a working knowledge of the basis for understanding the electronic structure and properties of the transition elements and their compounds. Therefore, theoretical features of the electronic structure of transition metal compounds are an important component of the training of both the experimental and theoretical chemist contributing solutions to problems in this area. Since this chemistry permeates industrial and biological chemistry as well as catalysis, solutions to problems in this field take on considerable importance. The field of transition metal chemistry is, indeed, fortunate that Isaac Bersuker, the leading contributor to the theory of transition metal electronic structure in the late period of the former Soviet Union, has translated and edited his numerous contributions published originally in Russian and combined them with new work into this modern English language text.

Isaac Bersuker became recognized as an authority in the Soviet Union on transition metal chemistry theory with publication of his 1962 book, which in many ways covered the same material that was published in English as An Introduction to Transition‐Metal Chemistry