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arXiv:1908.10938 · New Journal of Physics

Implications of pinned occupation numbers for natural orbital expansions: I. Generalizing the concept of active spaces

Christian Schilling, Carlos L. Benavides-Riveros, Alexandre Lopes, Tomasz Maciążek, Adam Sawicki

Published Dec 20, 2019• 15 citations
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Abstract

Abstract The concept of active spaces simplifies the description of interacting quantum many-body systems by restricting to a neighborhood of active orbitals around the Fermi level. The respective wavefunction ansatzes which involve all possible electron configurations of active orbitals can be characterized by the saturation of a certain number of Pauli constraints 0 ≤ n i ≤ 1 , identifying the occupied core orbitals (n i = 1) and the inactive virtual orbitals (n j = 0). In Part I, we generalize this crucial concept of active spaces by referring to the generalized Pauli constraints. To be more specific, we explain and illustrate that the saturation of any such constraint on fermionic occupation numbers characterizes a distinctive set of active electron configurations. A converse form of this selection rule establishes the basis for corresponding multiconfigurational wavefunction ansatzes. In Part II, we provide rigorous derivations of those findings. Moroever, we extend our results to non-fermionic multipartite quantum systems, revealing that extremal single-body information has always strong implications for the multipartite quantum state. In that sense, our work also confirms that pinned quantum systems define new physical entities and the presence of pinnings reflect the existence of (possibly hidden) ground state symmetries.

DOI
10.1088/1367-2630/ab64b0

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Fermionic natural occupation numbers (NON) do not only obey Pauli's famous exclusion principle, but are even further restricted to a polytope by the generalized Pauli constraints, conditions which follow from the fermionic exchange statistics. Whenever given NON are pinned to the polytope's boundary, the corresponding $N$-fermion quantum state $|{\ensuremath{\Psi}}_{N}\ensuremath{\rangle}$ simplifies due to a selection rule. We show analytically and numerically for the most relevant cases that this rule is stable for NON close to the boundary, if the NON are nondegenerate. In case of degeneracy, a modified selection rule is conjectured and its validity is supported. As a consequence, the recently found effect of quasipinning is physically relevant in the sense that its occurrence allows to approximately reconstruct $|{\ensuremath{\Psi}}_{N}\ensuremath{\rangle}$, its entanglement properties, and correlations from one-particle information. Our finding also provides the basis for a generalized Hartree-Fock method by a variational ansatz determined by the selection rule.

arXiv:1409.0019•Physical Review A•Feb 9, 2015•44 citations
Abstract The concept of active spaces simplifies the description of interacting quantum many-body systems by restricting to a neighborhood of active orbitals around the Fermi level. The respective wavefunction ansatzes which involve all possible electron configurations of active orbitals can be characterized by the saturation of a certain number of Pauli constraints 0 ≤ n i ≤ 1 , identifying the occupied core orbitals (n i = 1) and the inactive virtual orbitals (n j = 0). In Part I, we generalize this crucial concept of active spaces by referring to the generalized Pauli constraints. To be more specific, we explain and illustrate that the saturation of any such constraint on fermionic occupation numbers characterizes a distinctive set of active electron configurations. A converse form of this selection rule establishes the basis for corresponding multiconfigurational wavefunction ansatzes. In Part II, we provide rigorous derivations of those findings. Moroever, we extend our results to non-fermionic multipartite quantum systems, revealing that extremal single-body information has always strong implications for the multipartite quantum state. In that sense, our work also confirms that pinned quantum systems define new physical entities and the presence of pinnings reflect the existence of (possibly hidden) ground state symmetries.
Abstract We have explained and comprehensively illustrated in Part I (Schilling et al 2019 arXiv: 1908.10938 ) that the generalized Pauli constraints suggest a natural extension of the concept of active spaces. In the present Part I (Schilling et al 2019 arXiv: 1908.10938 )I, we provide rigorous derivations of the theorems involved therein. This will offer in particular deeper insights into the underlying mathematical structure and will explain why the saturation of generalized Pauli constraints implies a specific simplified structure of the corresponding many-fermion quantum state. Moreover, we extend the results of Part I (Schilling et al 2019 arXiv: 1908.10938 ) to non-fermionic multipartite quantum systems, revealing that extremal single-body information has always strong implications for the multipartite quantum state. In that sense, our work also confirms that pinned quantum systems define new physical entities and the presence of pinnings reflect the existence of (possibly hidden) ground state symmetries.
When the natural occupation numbers of a fermionic state saturate a generalized Pauli constraint, the state obeys a selection rule: only those configurations of natural orbitals that saturate the constraint themselves contribute. Pinning thus singles out an active space. The selection rule was proved for non-degenerate occupation numbers; for degenerate ones it was conjectured, and proved for one saturated constraint under an assumption checked only for the constraints known at the time. Here, it is proved for every generalized Pauli constraint, with no assumption, and also in the spin-adapted setting. The rule can only fail for the ordering constraints λj≥λj+1λ_j\geλ_{j+1}λj​≥λj+1​. Several saturated constraints are served by one basis whenever their common zero face contains a non-degenerate point. In practice, occupation numbers are quasipinned rather than pinned, and the rule survives with an explicit error bound.
The Pauli exclusion principle as constraint on fermionic occupation numbers is a consequence of the much deeper fermionic exchange statistics. Just recently, it was shown by Klyachko that this antisymmetry of fermionic wave functions leads to further restrictions on natural occupation numbers. These so-called generalized Pauli constraints (GPC) significantly strengthen Pauli's exclusion principle. Our first goal is to develop an understanding of the mathematical concepts behind Klyachko's work, in the context of quantum marginal problems. Afterwards, we explore the physical relevance of GPC and study concrete physical systems from that new viewpoint. In the first part of this thesis we review Klyachko's solution of the univariate quantum marginal problem. In particular we break his abstract derivation based on algebraic topology down to a more elementary level and reveal the geometrical picture behind it. The second part explores the possible physical relevance of GPC. We review the effect of pinning, i.e. the saturation of some GPC by given natural occupation numbers and explain its consequences. Although this effect would be quite spectacular we argue that pinning is unnatural. Instead, we conjecture the effect of quasipinning, defined by occupation numbers close to (but not exactly on) the boundary of the allowed region. In the third part we study concrete fermionic quantum systems from the new viewpoint of GPC. In particular, we compute the natural occupation numbers for the ground state of a family of interacting fermions in a harmonic potential. Intriguingly, we find that the occupation numbers are strongly quasipinned, even up to medium interaction strengths. We identify this as an effect of the lowest few energy eigenstates, which provides first insights into the mechanism behind quasipinning.
The Pauli exclusion principle requires that spin orbitals have occupations between zero and one. For pure quantum systems, however, the occupations of the spin orbitals are constrained by additional inequalities known as the generalized Pauli constraints. If the occupation numbers saturate (or nearly saturate) the generalized Pauli constraints, then the occupation numbers are said to be pinned (or quasi‐pinned) to the constraints. Here, we assess the complexity of electron correlation of excited states from the pinning or quasi‐pinning of the occupation numbers to the generalized Pauli constraints where the degree of pinning encodes information about the structure of the wave function including correlation and entanglement. Results are presented for three‐ and four‐electron atoms and molecules, the five‐electron cyclopentadienyl radical, and the seven‐electron Fenna‐Matthews‐Olson complex in green‐sulfur bacteria. The data shows that even when the ground‐state occupation numbers are pinned, the occupation numbers of excited states manifest pinned, quasi‐pinned, and unpinned behavior, reflecting the complexity of electron correlation and entanglement in excited states. © 2016 Wiley Periodicals, Inc.
We establish a toolbox for studying and applying spin-adapted generalized Pauli constraints (GPCs) in few-electron quantum systems. By exploiting the spin symmetry of realistic N -electron wave functions, the underlying one-body pure N -representability problem simplifies, allowing us to calculate the GPCs for larger system sizes than previously accessible. We then uncover and rigorously prove a superselection rule that highlights the significance of GPCs: whenever a spin-adapted GPC is (approximately) saturated—referred to as (quasi)pinning—the corresponding N -electron wave function assumes a simplified structure. Specifically, in a configuration interaction expansion based on natural orbitals only very specific spin configuration state functions may contribute. To assess the nontriviality of (quasi)pinning, we introduce a geometric measure that contrasts it with the (quasi)pinning induced by simple (spin-adapted) Pauli constraints. Applications to few-electron systems suggest that previously observed quasipinning largely stems from spin symmetries.
Fermionic natural occupation numbers (NON) do not only obey Pauli's famous exclusion principle, but are even further restricted to a polytope by the generalized Pauli constraints, conditions which follow from the fermionic exchange statistics. Whenever given NON are pinned to the polytope's boundary, the corresponding NNN-fermion quantum state $|{\ensuremath{\Psi}}_{N}\ensuremath{\rangle}$ simplifies due to a selection rule. We show analytically and numerically for the most relevant cases that this rule is stable for NON close to the boundary, if the NON are nondegenerate. In case of degeneracy, a modified selection rule is conjectured and its validity is supported. As a consequence, the recently found effect of quasipinning is physically relevant in the sense that its occurrence allows to approximately reconstruct $|{\ensuremath{\Psi}}_{N}\ensuremath{\rangle}$, its entanglement properties, and correlations from one-particle information. Our finding also provides the basis for a generalized Hartree-Fock method by a variational ansatz determined by the selection rule.