Diatomic Interaction Potential Theory

Diatomic Interaction Potential Theory, Volume 1: Fundamentals deals with the theoretical approaches to calculations for diatomic systems in their ground states. More specifically, this book considers the problem of calculating the wave function and energy for the lowest state of a system of N electrons moving in the field of two fixed point charges (the nuclei of a diatomic system) separated by a distance R.

Comprised of three chapters, this volume opens with an introduction to the nature of an interatomic interaction potential or potential energy curve. The separation of nuclear from electronic motions is considered, along with the methods used to measure potential energy curves. The next chapter presents a qualitative discussion of potential energy curves, with emphasis on the effects to be expected when two atomic systems are allowed to interact at large separation. The final chapter looks at the main approaches to schemes of calculation: variation theory, perturbation theory, the virial and Hellmann-Feynman theorems, local energy principles, and quantum statistical theories.
This monograph will be a useful resource for students and teachers of physical chemistry.

Contenu

Preface
Notes on Notation and Coordinate Systems
Contents of Volume 2
Chapter I Introduction to Potential Curves
A. Introduction
B. Separation of Nuclear from Electronic Motions

1. Center of Mass and Relative Motion
2. Born-Oppenheimer Separation
3. Adiabatic Treatment
4. Non-crossing Rule
5. Separation of Rotation
6. Correcting for Nuclear-Electronic Interaction
   C. Measurement of Potential Energy Curves
7. Spectroscopy
8. Scattering
9. Other Measurements
   Supplementary Bibliography
   Chapter II Qualitative Discussion of Potential Energy Curves
   A. Very Large Internuclear Distances
   B. Large Internuclear Distances
   C. Bond Region and Smaller R
   D. Forms for U(R)
10. Functional Forms
11. Theoretical Considerations
    Supplementary Bibliography
    Chapter III Methods of Calculation
    A. Variation Methods
12. General
13. Bounds
14. Correcting Expectation Values
15. Linear Variation
16. Single-Determinant Functions
17. Density Matrix
18. Configuration Interaction
19. Pair Functions and Correlated Wave Functions
    B. Perturbation Theory
20. General Formulas
21. Hartree-Fock Perturbation Theory
22. Improving a Determinantal Function
23. Perturbation Theory for Change of R
24. Double Perturbation Theory
    C. Virial Theorem
25. Scaling and the Virial Theorem
26. Consequences of the Virial Theorem
    D. Hellmann-Feynman Theorem
27. Hellmann-Feynman Theorem and Electrostatic Forces
28. Validity of the Theorem
29. Applications
30. Generalizations
    E. Local Energy Methods
31. Basic Formulas
32. Avoiding Integral Evaluation
    F. Quantum Statistical Calculations
33. Thomas-Fermi and Thomas-Fermi-Dirac Theories
34. Applications to Molecular Systems
35. Closed-Shell Systems
    Supplementary Bibliography
    General Bibliography
    Author Index
    Subject Index