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arXiv:0904.2009

The Pauli exclusion principle and beyond

Alexander A. Klyachko

Published Apr 13, 2009• 27 citations
arXivHTMLPDF

Abstract

The Pauli exclusion principle can be stated as inequality $\le 1$ for the electron density matrix $ρ$. Nowadays it is replaced by skew symmetry of the multi-electron wave function. The replacement leads to numerous additional constraints on $ρ$, which are discussed in this letter together with their physical implications, in particular for spin magnetic moment of a multi-electron system.

DOI
10.48550/arxiv.0904.2009

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The Pauli exclusion principle can be stated as inequality ≤1\le 1≤1 for the electron density matrix ρρρ. Nowadays it is replaced by skew symmetry of the multi-electron wave function. The replacement leads to numerous additional constraints on ρρρ, which are discussed in this letter together with their physical implications, in particular for spin magnetic moment of a multi-electron system.
The Pauli exclusion principle is a key postulate of the quantum theory and informs much of what we know about matter. In terms of electronic structure, the lone, deceptively simple mathematical requirement is that the total wave function be antisymmetric with respect to the exchange of any two electrons. However, visualizing the effect on the electron distribution presents a formidable challenge to students because of the complexity and number of variables involved. Approaches to gaining insight developed here include a quantitative analysis of two-dimensional configuration spaces as well as a qualitative assessment of interference patterns. For 2p x 1 2p y 1 states as representative examples, the analysis reveals that the Pauli principle directs electrons with opposing spins to codistribute along axes passing through the nucleus in the plane of the occupied orbitals. On the other hand, electrons with the same spin are never simultaneously in the same place or on the same axis; instead, they preferentially distribute in perpendicular directions.
This is the first scientific book devoted to the Pauli Exclusion Principle, which is a fundamental principle of quantum mechanics and is permanently applied in chemistry, physics, molecular biology and in physical astronomy. However, while the principle has been studied for more than 90 years, rigorous theoretical foundations still have not been established and many unsolved problems remain. Following an introduction and historical survey, this book discusses the still unresolved questions around this fundamental principle. For instance, why, according to the Pauli Exclusion Principle, are only symmetric and antisymmetric permutation symmetries for identical particles realized, while the Schrödinger equation is satisfied by functions with any permutation symmetry? Chapter 3 covers possible answers to this, while chapter 4 presents effective and elegant methods for finding the Pauli-allowed states in atomic, molecular and nuclear spectroscopy. Chapter 5 discusses parastatistics and fractional statistics, demonstrating that the quasiparticles in a periodical lattice, including excitons and magnons, are obeying modified parafermi statistics. With detailed appendices, The Pauli Exclusion Principle: Origin, Verifications and Applications is intended as a self-sufficient guide for graduate students and academic researchers in the fields of quantum mechanics, theoretical chemistry, physics, and applied mathematics. It will be a valuable resource for any reader interested in the foundations of quantum mechanics and its applications in areas such as atomic and molecular spectroscopy, spintronics, molecular biology, and applied fields of quantum information.