Hypervirial theorems (Q1820403)

A hypervirial theorem (HT) defines a commutation relation such as: Let \(\psi_ 0\) be an eigenfunction of the operator H with eigenvalue \(E_ 0\) and suppose that \(\psi\) satisfies \[ (1)\quad <\psi | [H,\omega]| \psi_ 0>=(E-E_ 0)<\psi | \omega \psi_ 0> \] for any linear operator \(\omega\). Then \(\psi\) is an eigenfunction of H with eigenvalue E. The diagonal form (DHT) of equation (1) is: \[ (2)\quad <\psi | [H,\omega]| \psi >=0. \] The name follows from the fact that if H is the hamiltonian operator for a N-particle system, then equation (2) becomes the well known virial theorem. HT may be used to check for the quantum mechanical models which cannot be exactly solved whether an approximation of the actual wave function is acceptable. This book presents in a comprehensive way for readers at a postgraduate level with a standard mathematical background the theoretical foundations of HT as well as their application to actual problems in quantum chemistry. In part A it is assumed that the domain and the range of all operators coincide with the entire Hilbert space corresponding to the physical system under study. The first chapter supplies HT and it is shown how the exact eigenfunctions of an hermitian operator satisfy HT. In chapter II the manner is discussed that DHT can give meaningful information about the properties of the functions obtained by the Rayleigh-Schrödinger perturbation theory (a variant of this perturbation method is considered in chapter VI). In chapter III it is shown how DHT allows to optimize trial functions in variational approximations. The purpose of chapter IV is to extend to HT the results of chapter III. The application to self- consistent field functions is discussed in chapter V. In part B the restriction that the domain of the hamiltonian operator contains the range of the hypervirial operator is removed. In this situation the importance of the different boundary conditions (BC) is first discussed (chapter VII). Then HT are reformulated for one dimensional finite systems with general BC (chapter VIII), Dirichlet BC (chapter IX), Neumann BC (chapter X) and finally for finite multidimensional systems (chapter XI). Some applications are given with numerical results. Two special topics are discussed: HT and statistical quantum mechanics. HT and semi-classical approximation. The notions required to understand the main text are given in ten appendices. Seventeen programms written with two exceptions for the programmable Texas Ti 58/59 computer complete this work. Each chapter is supported by many references. There are few misprints but the Neumann BC are wrongly called the von Neumann BC.