Chapter 10. General Molecules and Molecular Aggregates
Published Online: 22 JUN 2009
DOI: 10.1002/9783527627486.ch10
Copyright © 2009 Wiley-VCH Verlag GmbH & Co. KGaA
Book Title
Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science
Additional Information
How to Cite
Reiher, M. and Wolf, A. (2009) General Molecules and Molecular Aggregates, in Relativistic Quantum Chemistry: The Fundamental Theory of Molecular Science, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, Germany. doi: 10.1002/9783527627486.ch10
Publication History
- Published Online: 22 JUN 2009
- Published Print: 14 JAN 2009
ISBN Information
Print ISBN: 9783527312924
Online ISBN: 9783527627486
- Summary
- Chapter
Keywords:
- general molecules;
- molecular aggregates;
- molecular spinors;
- Dirac–Hartree–Fock electronic energy;
- molecular one-electron integrals;
- molecular two-electron integrals;
- Dirac–Hartree–Fock–Roothaan matrix equations;
- analytic gradients;
- post-Hartree–Fock methods
Summary
After having derived a relativistic four-component Hamiltonian operator in chapter 8 — often called a ‘fully relativistic’ Hamiltonian although fundamental requirements of special relativity have been given up (no absolute time and Lorentz covariance) — and having employed it for spherically symmetric atoms, it is now appropriate to proceed to the case of general molecules. Here, we need to introduce suitable approximations for the one-electron functions of molecular systems. Results and inventions of the historically earlier developed nonrelativistic theory are transferred to the relativistic regime. However, a couple of subtleties like variational collapse, kinetic balance and the role of the negative-energy states need to be taken care of.