Andrew Cooksy - Physical Chemistry: Quantum Chemistry and Molecular Interactions

and Molecular Interactions

and Molecular Interactions

Andrew Cooksy

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Library of Congress Cataloging-in-Publication Data

Cooksy, Andrew.

Physical chemistry : quantum chemistry and molecular interactions / Andrew Cooksy. pages cm

Includes index.

ISBN-13: 978-0-321-81416-6

ISBN-10: 0-321-81416-9

1. Chemistry, Physical and theoretical--Textbooks. 2. Quantum chemistry--Textbooks. 3. Molecular dynamics--Textbooks. I. Title.

QD453.3.C655 2014

641--dc23

2012037314

1 2 3 4 5 6 7 8 9 10RRD16 15 14 13 12

ISBN-10: 0-321-81416-9

ISBN-13: 978-0-321-81416-6

www.pearsonhighered.com

To Mary, Wesley, and Owen

our great creative Mother, while she amuses us with apparently working in the broadest sunshine, is yet severely careful to keep her own secrets, and, in spite of her pretended openness, shows us nothing but results.

Nathaniel Hawthorne (18041864) The Birthmark

This book is intended to provide students with a detailed guide to the reasoning that forms the basis for physical chemistrythe framework that unites all chemistry. The study of physical chemistry gives us the opportunity to look at our science as an integrated whole, with each concept connected to the next. My goal has been to trace those connections, step-by-step whenever possible, to show how each new concept makes sense given its place in the framework.

Because its ideas build upon each other in this way, physical chemistry can serve as the foundation for an intuitive understanding of chemistry in all its forms, whether synthesizing new compounds, analyzing samples in a forensic laboratory, or studying the properties of novel materials. To that end, this book emphasizes the shared, fundamental principles of chemistry, showing how we can justify the form and behavior of complex chemical systems by applying the laws of mathematics and physics to the structures of individual particles and then extrapolating to larger systems. We learn physical chemistry so that we can recognize these fundamental principles when we run into them in our other courses and in our careers. The relevance of this discipline extends beyond chemistry to engineering, physics, biology, and medicine: any field in which the molecular structure of matter is important.

A key step toward cultivating an intuition about chemistry is a thorough and convincing presentation of these fundamentals. When we see not only what the ideas are, but also how they link together, those ideas become more discernible when we examine a new chemical system or process. The following features of this text seek to achieve that objective.

• My aim is to provide a rigorous treatment of the subject in a relaxed style. A combination of qualitative summaries and annotated, step-by-step derivations illuminates the logic connecting the theory to the parameters that we can measure by experiment. Although we use a lot of math to justify the theory we are developing, the math will always make sense if we look at it carefully. We take advantage of this to strengthen our confidence in the results and our understanding of how the math relates to the physics. Nothing is more empowering in physical chemistry than finding that you can successfully predict a phenomenon using both mathematics and a qualitative physical argument. The manifestation of atomic and molecular structure in bulk properties of materials is a theme that informs the unhurried narrative throughout the text.