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Chemical bonding is a nonlocal phenomenon that binds atoms into molecules. Its ubiquitous presence in chemistry, however, stands in stark contrast to its ambiguous definition and the lack of a universal perspective for its understanding. In this work, we rationalize and characterize chemical bonding through the lens of an equally nonlocal concept from quantum information, the orbital entanglement. We introduce maximally entangled atomic orbitals (MEAOs) whose entanglement pattern is shown to recover both Lewis (two-center) and beyond-Lewis (multicenter) structures, with multipartite entanglement serving as a comprehensive index of bond strength. Our unifying framework for bonding analyses is effective not only for equilibrium geometries but also for transition states in chemical reactions and complex phenomena such as aromaticity. It also has the potential to elevate the Hilbert space atomic partitioning to match the prevalent real-space partitioning in the theory of atoms in molecules. Accordingly, our work opens new pathways for understanding fuzzy chemical concepts using rigorous, quantitative descriptors from quantum information., Comment: 9+7 pages, 5+5 figures

The Pauli exclusion principle is fundamental to understanding electronic quantum systems. It namely constrains the expected occupancies $n_i$ of orbitals $\varphi_i$ according to $0 \leq n_i \leq 2$. In this work, we first refine the underlying one-body $N$-representability problem by taking into account simultaneously spin symmetries and a potential degree of mixedness $\boldsymbol w$ of the $N$-electron quantum state. We then derive a comprehensive solution to this problem by using basic tools from representation theory, convex analysis and discrete geometry. Specifically, we show that the set of admissible orbital one-body reduced density matrices is fully characterized by linear spectral constraints on the natural orbital occupation numbers, defining a convex polytope $\Sigma_{N,S}(\boldsymbol w) \subset [0,2]^d$. These constraints are independent of $M$ and the number $d$ of orbitals, while their dependence on $N, S$ is linear, and we can thus calculate them for arbitrary system sizes and spin quantum numbers. Our results provide a crucial missing cornerstone for ensemble density (matrix) functional theory.

It is the ultimate goal of this work to foster synergy between quantum chemistry and the flourishing field of quantum information theory. For this, we first translate quantum information concepts such as entanglement and correlation into the context of quantum chemical systems. In particular, we establish two conceptually distinct perspectives on `electron correlation' leading to a notion of orbital and particle correlation. We then demonstrate that particle correlation equals total orbital correlation minimized over all orbital bases. Accordingly, particle correlation resembles the minimal, thus intrinsic, complexity of many-electron wave functions while orbital correlation quantifies their complexity relative to a basis. We illustrate these concepts of intrinsic and extrinsic correlation complexity in molecular systems, which also manifests the crucial link between the two correlation pictures. Our results provide theoretical justification for the long-favored natural orbitals for simplifying electronic structures, and open new pathways for developing more efficient approaches towards the electron correlation problem.

The simultaneous treatment of static and dynamical correlations in strongly-correlated electron systems is a critical challenge. In particular, finding a universal scheme for identifying a single-particle orbital basis that minimizes the representational complexity of the many-body wavefunction is a formidable and longstanding problem. As a substantial contribution towards its solution, we show that the total orbital correlation actually reveals and quantifies the intrinsic complexity of the wavefunction,once it is minimized via orbital rotations. To demonstrate the power of this concept in practice, an iterative scheme is proposed to optimize the orbitals by minimizing the total orbital correlation calculated by the tailored coupled cluster singles and doubles (TCCSD) ansatz. The optimized orbitals enable the limited TCCSD ansatz to capture more non-trivial information of the many-body wavefunction, indicated by the improved wavefunction and energy. An initial application of this scheme shows great improvement of TCCSD in predicting the singlet ground state potential energy curves of the strongly correlated C$_{\rm 2}$ and Cr$_{\rm 2}$ molecule., Comment: Close to published version

The extension of the Rayleigh-Ritz variational principle to ensemble states $\rho_{\mathbf{w}}\equiv\sum_k w_k |\Psi_k\rangle \langle\Psi_k|$ with fixed weights $w_k$ lies ultimately at the heart of several recent methodological developments for targeting excitation energies by variational means. Prominent examples are density and density matrix functional theory, Monte Carlo sampling, state-average complete active space self-consistent field methods and variational quantum eigensolvers. In order to provide a sound basis for all these methods and to improve their current implementations, we prove the validity of the underlying critical hypothesis: Whenever the ensemble energy is well-converged, the same holds true for the ensemble state $\rho_{\mathbf{w}}$ as well as the individual eigenstates $|\Psi_k\rangle$ and eigenenergies $E_k$. To be more specific, we derive linear bounds $d_-\Delta{E}_{\mathbf{w}} \leq \Delta Q \leq d_+ \Delta{E}_{\mathbf{w}}$ on the errors $\Delta Q $ of these sought-after quantities. A subsequent analytical analysis and numerical illustration proves the tightness of our universal inequalities. Our results and particularly the explicit form of $d_{\pm}\equiv d_{\pm}^{(Q)}(\mathbf{w},\mathbf{E})$ provide valuable insights into the optimal choice of the auxiliary weights $w_k$ in practical applications., Comment: 23+7 pages, 9 figures, to appear on Quantum

Automated active space selection is arguably one of the most challenging and essential aspects of multiconfigurational methods. In this work we propose an effective quantum information-assisted complete active space optimization (QICAS) scheme. What sets QICAS apart from other correlation-based selection schemes is (i) the use of unique measures from quantum information that assess the correlation in electronic structures in an unambiguous and predictive manner, and (ii) an orbital optimization step that minimizes the correlation discarded by the active space approximation. Equipped with these features QICAS yields for smaller correlated molecules sets of optimized orbitals with respect to which the CASCI energy reaches the corresponding CASSCF energy within chemical accuracy. For more challenging systems such as the Chromium dimer, QICAS offers an excellent starting point for CASSCF by greatly reducing the number of iterations required for numerical convergence. Accordingly, our study validates a profound empirical conjecture: the energetically optimal non-active spaces are predominantly those that contain the least entanglement., Comment: Close to published version

The weighted subspace-search variational quantum eigensolver (SSVQE) is a prominent algorithm for calculating excited-state properties of molecular quantum systems. In this work, we elaborate on some of its fundamental features with the aim of improving its practical realization. First, we demonstrate that the initial ans\"atze for various excited states could be prepared into a single pure state through a minimal number of ancilla qubits, followed by the optimization of a subsequent global unitary rotation in the targeted subspace. Since the ancillas' sole purpose is to purify an underlying ensemble $\rho_{\boldsymbol{w}}$ state with spectral weights $\boldsymbol{w}$, their measurement would just collapse $\rho_{\boldsymbol{w}}$ with probabilities $w_j$ to one of its eigenstates $|\Psi_j \rangle$. We thus observe that our realization of SSVQE is equivalent to the original SSVQE improved by importance sampling. Then, we elaborate by numerical means on the potential influence of the auxiliary weights $\boldsymbol{w}$ on the accuracy of the sought-after eigenstates and eigenenergies. Clear trends are discovered which are contrasted with some recent mathematical results concerning the ensemble variational principle that underlies SSVQE., Comment: 21 pages, 8 figures. The title has been changed

In [arXiv:2207.03377] the first closed formula of a faithful entanglement measure applicable to realistic electron systems has been derived. In the present work, we build on this key achievement with the ultimate goal of guiding the development of quantum technologies. For this, we first elucidate the process of entanglement swapping in electron systems such as atoms, molecules or solid bodies. This clearly demonstrates the necessity of both the reference to localized few-orbital subsystems and the implementation of the number-parity superselection rule. Accordingly, in virtue of Wick's theorem, we then provide a fully analytical study of the true physical entanglement between sites in free electron chains. In that sense, we break the common paradigm of restricting such analytical analyses to unitarily invariant settings, i.e. bipartitions of the chain into rather impractical, macroscopically large subsystems. We then upgrade this model to a hydrogen ring of interacting electrons and construct the sought-after localized orbitals. For both systems, we confirm the presence of long-distance entanglement, provided the filling fractions are sufficiently low/high., Comment: Close to published version

The leading terms in the large-$R$ asymptotics of the functional of the one-electron reduced density matrix for the ground-state energy of the H$_2$ molecule with the internuclear separation $R$ is derived thanks to the solution of the phase dilemma at the $R \to \infty$ limit. At this limit, the respective natural orbitals (NOs) are given by symmetric and antisymmetric combinations of "half-space" orbitals with the corresponding natural amplitudes of the same amplitudes but opposite signs. Minimization of the resulting explicit functional yields the large-$R$ asymptotics for the occupation numbers of the weakly occupied NOs and the $C_6$ dispersion coefficient. The highly accurate approximates for the radial components of the $p$-type "half-space" orbitals and the corresponding occupation numbers (that decay like $R^{-6}$), which are available for the first time thanks to the development of the present formalism, have some unexpected properties., Comment: close to published version; selected as "Editor's Pick"

To advance the foundation of one-particle reduced density matrix functional theory (1RDMFT) we refine and relate some of its fundamental features and underlying concepts. We define by concise means the scope of a 1RDMFT, identify its possible natural variables and explain how symmetries could be exploited. In particular, for systems with time-reversal symmetry, we explain why there exist six equivalent universal functionals, prove concise relations among them and conclude that the important notion of $v$-representability is relative to the scope and choice of variable. All these fundamental concepts are then comprehensively discussed and illustrated for the Hubbard dimer and its generalization to arbitrary pair interactions $W$. For this, we derive by analytical means the pure and ensemble functionals with respect to both the real- and complex-valued Hilbert space. The comparison of various functionals allows us to solve the underlying $v$-representability problems analytically and the dependence of its solution on the pair interaction is demonstrated. Intriguingly, the gradient of each universal functional is found to always diverge repulsively on the boundary of the domain. In that sense, this key finding emphasizes the universal character of the fermionic exchange force, recently discovered and proven in the context of translationally-invariant one-band lattice models.

We present symQV, a symbolic execution framework for writing and verifying quantum computations in the quantum circuit model. symQV can automatically verify that a quantum program complies with a first-order specification. We formally introduce a symbolic quantum program model. This allows to encode the verification problem in an SMT formula, which can then be checked with a delta-complete decision procedure. We also propose an abstraction technique to speed up the verification process. Experimental results show that the abstraction improves symQV's scalability by an order of magnitude to quantum programs with 24 qubits (a 2^24-dimensional state space)., Comment: This is the extended version of a paper with the same title that appeared at FM 2023. Tool available at doi.org/10.5281/zenodo.7400321

We initiate the recently proposed $\boldsymbol{w}$-ensemble one-particle reduced density matrix functional theory ($\boldsymbol{w}$-RDMFT) by deriving the first functional approximations and illustrate how excitation energies can be calculated in practice. For this endeavour, we first study the symmetric Hubbard dimer, constituting the building block of the Hubbard model, for which we execute the Levy-Lieb constrained search. Second, due to the particular suitability of $\boldsymbol{w}$-RDMFT for describing Bose-Einstein condensates, we demonstrate three conceptually different approaches for deriving the universal functional in a homogeneous Bose gas for arbitrary pair interaction in the Bogoliubov regime. Remarkably, in both systems the gradient of the functional is found to diverge repulsively at the boundary of the functional's domain, extending the recently discovered Bose-Einstein condensation force to excited states. Our findings highlight the physical relevance of the generalized exclusion principle for fermionic and bosonic mixed states and the curse of universality in functional theories., Comment: Application of w-RDMFT which has been proposed in arXiv:2204.12715; close to published version

Entanglement is one of the most fascinating concepts of modern physics. In striking contrast to its abstract, mathematical foundation, its practical side is, however, remarkably underdeveloped. Even for systems of just two orbitals or sites no faithful entanglement measure is known yet. By exploiting the spin symmetries of realistic many-electron systems, we succeed in deriving a closed formula for the relative entropy of entanglement between electron orbitals. Its broad applicability in the quantum sciences is demonstrated: (i) in light of the second quantum revolution, it quantifies the true physical entanglement by incorporating the crucial fermionic superselection rule (ii) an analytic description of the long-distance entanglement in free electron chains is found, refining Kohn's locality principle (iii) the bond-order wave phase in the extended Hubbard model can be confirmed, and (iv) the quantum complexity of common molecular bonding structures could be marginalized through orbital transformations, thus rationalizing zero-seniority wave function ansatzes.

The second quantum revolution is all about exploiting the quantum nature of atoms and molecules to execute quantum information processing tasks. To support this growing endeavor and by anticipating the key role of quantum chemistry therein, our work establishes a toolbox for systematically exploring, quantifying and dissecting correlation effects in quantum chemical systems. By utilizing the geometric picture of quantum states we compare -- on a unified basis and in an operationally meaningful way -- total, quantum and classical correlation and entanglement in molecular ground states. To maximize the quantum informational resourcefulness of molecules an orbital optimization scheme is provided, leading to a paradigm-shifting insight: A single covalent bond equates to the entanglement $2\ln(2)$. This novel and more versatile perspective on electronic structure suggests a generalization of valence bond theory, overcoming deficiencies of modern chemical bonding theories., Comment: Close to published version

Motivated by the Penrose-Onsager criterion for Bose-Einstein condensation we propose a functional theory for targeting low-lying excitation energies of bosonic quantum systems through the one-particle picture. For this, we employ an extension of the Rayleigh-Ritz variational principle to ensemble states with spectrum $\boldsymbol{w}$ and prove a corresponding generalization of the Hohenberg-Kohn theorem: The underlying one-particle reduced density matrix determines all properties of systems of $N$ identical particles in their $\boldsymbol{w}$-ensemble states. Then, to circumvent the $v$-representability problem common to functional theories, and to deal with energetic degeneracies, we resort to the Levy-Lieb constrained search formalism in combination with an exact convex relaxation. The corresponding bosonic one-body $\boldsymbol{w}$-ensemble $N$-representability problem is solved comprehensively. Remarkably, this reveals a complete hierarchy of bosonic exclusion principle constraints in conceptual analogy to Pauli's exclusion principle for fermions and recently discovered generalizations thereof., Comment: In particular, bosonic counterpart of fermionic w-RDMFT (arXiv:2106.02560, arXiv:2106.03918) is presented; v2: title has been changed, new section proving a generalization of the Hohenberg-Kohn theorem for w-RDMFT has been added

In [Phys. Rev. Lett. 128, 013001 (2022)] a novel ground state method was proposed. It has been suggested that this $i$-DMFT would be a method within one-particle reduced density matrix functional theory (DMFT), capable of describing accurately molecules at various geometries with an information-theoretical nature. We reassess this work and its suggestions from a conceptual and practical point of view, leading to the following conclusions: i) A method which assigns to each molecule $\mathcal{M}$ its own functional $\mathcal{F}_{\!\mathcal{M}}$ is not a functional theory (striking violation of "universality") ii) even for the simplest systems $i$-DMFT yields incorrect one-particle reduced density matrices and iii) the use of an information-theoretical concept to describe molecular dissociation limits was not essential. The latter insight may help to fix the deficiency of $i$-DMFT to not reproduce correctly the smaller occupation numbers and thus to not recover the important dynamic correlations., Comment: Comments are very welcome!

State-average calculations based on mixture of states are increasingly being exploited across chemistry and physics as versatile procedures for addressing excitations of quantum many-body systems. If not too many states should need to be addressed, calculations performed on individual states is also a common option. Here we show how the two approaches can be merged into one method, dealing with a generalized yet single pure state. Implications in electronic structure calculations are discussed and for quantum computations are pointed out., Comment: 9 pages, additional calculation

In [Phys. Rev. Lett. 127, 023001 (2021)] a reduced density matrix functional theory (RDMFT) has been proposed for calculating energies of selected eigenstates of interacting many-fermion systems. Here, we develop a solid foundation for this so-called $\boldsymbol{w}$-RDMFT and present the details of various derivations. First, we explain how a generalization of the Ritz variational principle to ensemble states with fixed weights $\boldsymbol{w}$ in combination with the constrained search would lead to a universal functional of the one-particle reduced density matrix. To turn this into a viable functional theory, however, we also need to implement an exact convex relaxation. This general procedure includes Valone's pioneering work on ground state RDMFT as the special case $\boldsymbol{w}=(1,0,\ldots)$. Then, we work out in a comprehensive manner a methodology for deriving a compact description of the functional's domain. This leads to a hierarchy of generalized exclusion principle constraints which we illustrate in great detail. By anticipating their future pivotal role in functional theories and to keep our work self-contained, several required concepts from convex analysis are introduced and discussed., Comment: published version; in particular various derivations of the letter arXiv:2106.02560 are provided

We propose and work out a reduced density matrix functional theory (RDMFT) for calculating energies of eigenstates of interacting many-electron systems beyond the ground state. Various obstacles which historically have doomed such an approach to be unfeasible are overcome. First, we resort to a generalization of the Ritz variational principle to ensemble states with fixed weights. This in combination with the constrained search formalism allows us to establish a universal functional of the one-particle reduced density matrix. Second, we employ tools from convex analysis to circumvent the too involved N-representability constraints. Remarkably, this identifies Valone's pioneering work on RDMFT as a special case of convex relaxation and reveals that crucial information about the excitation structure is contained in the functional's domain. Third, to determine the crucial latter object, a methodology is developed which eventually leads to a generalized exclusion principle. The corresponding linear constraints are calculated for systems of arbitrary size., Comment: to appear in Phys. Rev. Lett

From a geometric point of view, Pauli's exclusion principle defines a hypersimplex. This convex polytope describes the compatibility of $1$-fermion and $N$-fermion density matrices, therefore it coincides with the convex hull of the pure $N$-representable $1$-fermion density matrices. Consequently, the description of ground state physics through $1$-fermion density matrices may not necessitate the intricate pure state generalized Pauli constraints. In this article, we study the generalization of the $1$-body $N$-representability problem to ensemble states with fixed spectrum $\mathbf{w}$, in order to describe finite-temperature states and distinctive mixtures of excited states. By employing ideas from convex analysis and combinatorics, we present a comprehensive solution to the corresponding convex relaxation, thus circumventing the complexity of generalized Pauli constraints. In particular, we adapt and further develop tools such as symmetric polytopes, sweep polytopes, and Gale order. For both fermions and bosons, generalized exclusion principles are discovered, which we determine for any number of particles and dimension of the $1$-particle Hilbert space. These exclusion principles are expressed as linear inequalities satisfying hierarchies determined by the non-zero entries of $\mathbf{w}$. The two families of polytopes resulting from these inequalities are part of the new class of so-called lineup polytopes., Comment: 59 pages, 17 figures, 3 appendices Version 2: several minor changes and fixes, now the source files include two rst files containing the obtained generalized exclusion principles as linear inequalities

One-particle reduced density matrix functional theory would potentially be the ideal approach for describing Bose-Einstein condensates. It namely replaces the macroscopically complex wavefunction by the simple one-particle reduced density matrix, therefore provides direct access to the degree of condensation and still recovers quantum correlations in an exact manner. We eventually initiate and establish this novel theory by deriving the respective universal functional $\mathcal{F}$ for general homogeneous Bose-Einstein condensates with arbitrary pair interaction. Most importantly, the successful derivation necessitates a particle-number conserving modification of Bogoliubov theory and a solution of the common phase dilemma of functional theories. We then illustrate this novel approach in several bosonic systems such as homogeneous Bose gases and the Bose-Hubbard model. Remarkably, the general form of $\mathcal{F}$ reveals the existence of a universal Bose-Einstein condensation force which provides an alternative and more fundamental explanation for quantum depletion., Comment: close to published version

The operator algebra of fermionic modes is isomorphic to that of qubits, the difference between them is twofold: the embedding of subalgebras corresponding to mode subsets and multiqubit subsystems on the one hand, and the parity superselection in the fermionic case on the other. We discuss these two fundamental differences extensively, and illustrate these through the Jordan--Wigner representation in a coherent, self-contained, pedagogical way, from the point of view of quantum information theory. Our perspective leads us to develop useful new tools for the treatment of fermionic systems, such as the fermionic (quasi-)tensor product, fermionic canonical embedding, fermionic partial trace, fermionic products of maps and fermionic embeddings of maps. We formulate these by direct, easily applicable formulas, without mode permutations, for arbitrary partitionings of the modes. It is also shown that fermionic reduced states can be calculated by the fermionic partial trace, containing the proper phase factors. We also consider variants of the notions of fermionic mode correlation and entanglement, which can be endowed with the usual, local operation based motivation, if the parity superselection rule is imposed. We also elucidate some other fundamental points, related to joint map extensions, which make the parity superselection inevitable in the description of fermionic systems., Comment: some typos corrected, page makeup improved, 62 pages

A recent development in quantum chemistry has established the quantum mutual information between orbitals as a major descriptor of electronic structure. This has already facilitated remarkable improvements of numerical methods and may lead to a more comprehensive foundation for chemical bonding theory. Building on this promising development, our work provides a refined discussion of quantum information theoretical concepts by introducing the physical correlation and its separation into classical and quantum parts as distinctive quantifiers of electronic structure. In particular, we succeed in quantifying the entanglement. Intriguingly, our results for different molecules reveal that the total correlation between orbitals is mainly classical, raising questions about the general significance of entanglement in chemical bonding. Our work also shows that implementing the fundamental particle number superselection rule, so far not accounted for in quantum chemistry, removes a major part of correlation and entanglement previously seen. In that respect, realizing quantum information processing tasks with molecular systems might be more challenging than anticipated., Comment: Close to published version

The realization of Bose-Einstein condensation in ultracold trapped gases has led to a revival of interest in that fascinating quantum phenomenon. This experimental achievement necessitated both extremely low temperatures and sufficiently weak interactions. Particularly in reduced spatial dimensionality even an infinitesimal interaction immediately leads to a departure to quasi-condensation. We propose a system of strongly interacting bosons which overcomes those obstacles by exhibiting a number of intriguing related features: (i) The tuning of just a single control parameter drives a transition from quasi-condensation to complete condensation, (ii) the destructive influence of strong interactions is compensated by the respective increased mobility, (iii) topology plays a crucial role since a crossover from one- to `infinite'-dimensionality is simulated, (iv) a ground state gap opens which makes the condensation robust to thermal noise. Remarkably, all these features can be derived by analytical and exact numerical means despite the non-perturbative character of the system., Comment: close to published version; title has been changed

Based on a generalization of Hohenberg-Kohn's theorem, we propose a ground state theory for bosonic quantum systems. Since it involves the one-particle reduced density matrix $\gamma$ as a natural variable but still recovers quantum correlations in an exact way it is particularly well-suited for the accurate description of Bose-Einstein condensates. As a proof of principle we study the building block of optical lattices. The solution of the underlying $v$-representability problem is found and its peculiar form identifies the constrained search formalism as the ideal starting point for constructing accurate functional approximations: The exact functionals for this $N$-boson Hubbard dimer and general Bogoliubov-approximated systems are determined. The respective gradient forces are found to diverge in the regime of Bose-Einstein condensation, $\nabla_{\gamma} \mathcal{F} \propto 1/\sqrt{1-N_{\mathrm{BEC}}/N}$, providing a natural explanation for the absence of complete BEC in nature.

The interplay between electron interaction and geometry in a molecular system can lead to rather paradoxical situations. The prime example is the dissociation limit of the hydrogen molecule: While a significant increase of the distance $r$ between the two nuclei marginalizes the electron-electron interaction, the exact ground state does, however, not take the form of a single Slater determinant. By first reviewing and then employing concepts from quantum information theory, we resolve this paradox and its generalizations to more complex systems in a quantitative way. To be more specific, we illustrate and prove that thermal noise due to finite, possibly even just infinitesimally low, temperature $T$ will destroy the entanglement beyond a critical separation distance $r_{\mathrm{crit}}$($T$) entirely. Our analysis is comprehensive in the sense that we simultaneously discuss both total correlation and entanglement in the particle picture as well as in the orbital/mode picture. Our results reveal a conceptually new characterization of static and dynamical correlation in ground states by relating them to the (non)robustness of correlation with respect to thermal noise., Comment: title has been modified, close to published version

We have explained and comprehensively illustrated in Part I that the generalized Pauli constraints suggest a natural extension of the concept of active spaces. In the present Part II, 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 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., Comment: Part II of arXiv:1908.10938

The concept of active spaces simplifies the description of interacting quantum many-body systems by restricting to a neighbourhood 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 $0 \leq n_i \leq 1$, 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.

For translationally invariant one-band lattice models, we exploit the ab initio knowledge of the natural orbitals to simplify reduced density matrix functional theory (RDMFT). Striking underlying features are discovered: First, within each symmetry sector, the interaction functional $\mathcal{F}$ depends only on the natural occupation numbers $\bf{n}$. The respective sets $\mathcal{P}^1_N$ and $\mathcal{E}^1_N$ of pure and ensemble $N$-representable one-matrices coincide. Second, and most importantly, the exact functional is strongly shaped by the geometry of the polytope $\mathcal{E}^1_N \equiv \mathcal{P}^1_N $, described by linear constraints $D^{(j)}(\bf{n})\geq 0$. For smaller systems, it follows as $\mathcal{F}[\bf{n}]=\sum_{i,i'} \overline{V}_{i,i'} \sqrt{D^{(i)}(\bf{n})D^{(i')}(\bf{n})}$. This generalizes to systems of arbitrary size by replacing each $D^{(i)}$ by a linear combination of $\{D^{(j)}(\bf{n})\}$ and adding a non-analytical term involving the interaction $\hat{V}$. Third, the gradient $\mathrm{d}\mathcal{F}/\mathrm{d}\bf{n}$ is shown to diverge on the boundary $\partial\mathcal{E}^1_N$, suggesting that the fermionic exchange symmetry manifests itself within RDMFT in the form of an "exchange force". All findings hold for systems with non-fixed particle number as well and $\hat{V}$ can be any $p$-particle interaction. As an illustration, we derive the exact functional for the Hubbard square., Comment: published version

A crucial theorem in Reduced Density Matrix Functional Theory (RDMFT) suggests that the universal pure and ensemble functional coincide on their common domain of pure N-representable one-matrices. We refute this by a comprehensive analysis of the geometric picture underlying Levy's constrained search. Moreover, we then show that the ensemble functional follows instead as the lower convex envelop of the pure functional. It is particularly remarkable that the pure functional determines the ensemble functional even outside its own domain of pure N-representable one-matrices. From a general perspective, this demonstrates that relaxing pure RDMFT to ensemble RDMFT does not necessarily circumvent the complexity of the one-body pure N-representability conditions (generalized Pauli constraints). Instead, the complexity may simply be transferred from the underlying space of pure N-representable one-matrices to the structure of the universal one-matrix functional., Comment: version as published in Communications of Journal of Chemical Physics

Fermionic natural occupation numbers do not only obey Pauli's exclusion principle but are even stronger restricted by so-called generalized Pauli constraints. Whenever given natural occupation numbers lie on the boundary of the allowed region the corresponding $N$-fermion quantum state has a significantly simpler structure. We recall the recently proposed natural extension of the Hartree-Fock ansatz based on this structural simplification. This variational ansatz is tested for the lithium atom. Intriguingly, the underlying mathematical structure yields universal geometrical bounds on the correlation energy reconstructed by this ansatz., Comment: Contribution to the special issue dedicated to professor Michael Springborg on the occasion of his 60th birthday, 7 pages

The dependence of the (quasi-)saturation of the generalized Pauli constraints on the pair potential is studied for ground states of few-fermion systems. For this, we consider spinless fermions in one dimension which are harmonically confined and interact by pair potentials of the form $|x_i-x_j|^s$ with $-1 \leq s\leq 5$. We use the Density Matrix Renormalization Group approach and large orbital basis to achieve the convergence on more than ten digits of both the variational energy and the natural occupation numbers. Our results confirm that the conflict between energy minimization and fermionic exchange symmetry results in a universal and non-trivial quasi-saturation of the generalized Pauli constraints (\emph{quasipinning}), implying tremendous structural simplifications of the fermionic ground state for all $s$. Those numerically exact results are complemented by an analytical study based on a self-consistent perturbation theory which we develop for this purpose. The respective results for the weak coupling regime eventually elucidate the singular behaviour found for the specific values $s=2,4,\ldots$, resulting in an extremely strong quasipinning., Comment: published version

The natural occupation numbers of fermionic systems are subject to non-trivial constraints, which include and extend the original Pauli principle. A recent mathematical breakthrough has clarified their mathematical structure and has opened up the possibility of a systematic analysis. Early investigations have found evidence that these constraints are exactly saturated in several physically relevant systems, e.g., in a certain electronic state of the Beryllium atom. It has been suggested that in such cases, the constraints, rather than the details of the Hamiltonian, dictate the system's qualitative behaviour. Here, we revisit this question with state-of-the-art numerical methods for small atoms. We find that the constraints are, in fact, not exactly saturated, but that they lie much closer to the surface defined by the constraints than the geometry of the problem would suggest. While the results seem incompatible with the statement that the generalized Pauli constraints drive the behaviour of these systems, they suggest that the qualitatively correct wave-function expansions can in some systems already be obtained on the basis of a limited number of Slater determinants, which is in line with numerical evidence from quantum chemistry., Comment: published version

For $N$ hard-core bosons on an arbitrary lattice with $d$ sites and independent of additional interaction terms we prove that the hard-core constraint itself already enforces a universal upper bound on the Bose-Einstein condensate given by $N_{max}=(N/d)(d-N+1)$. This bound can only be attained for one-particle states $|\varphi\rangle$ with equal amplitudes with respect to the hard-core basis (sites) and when the corresponding $N$-particle state $|\Psi\rangle$ is maximally delocalized. This result is generalized to the maximum condensate possible within a given sublattice. We observe that such maximal local condensation is only possible if the mode entanglement between the sublattice and its complement is minimal. We also show that the maximizing state $|\Psi\rangle$ is related to the ground state of a bosonic `Hubbard star' showing Bose-Einstein condensation., Comment: to appear in Phys. Rev. B

The possible compatibility of density matrices for single-party subsystems is described by linear constraints on their respective spectra. Whenever some of those quantum marginal constraints are saturated, the total quantum state has a specific, simplified structure. We prove that these remarkable global implications of extremal local information are stable, i.e. they hold approximately for spectra close to the boundary of the allowed region. Application of this general result to fermionic quantum systems allows us to characterize natural extensions of the Hartree-Fock ansatz and to quantify their accuracy by resorting to one-particle information, only: The fraction of the correlation energy not recovered by such an ansatz can be estimated from above by a simple geometric quantity in the occupation number picture.

The concept of correlation is central to all approaches that attempt the description of many-body effects in electronic systems. Multipartite correlation is a quantum information theoretical property that is attributed to quantum states independent of the underlying physics. In quantum chemistry, however, the correlation energy (the energy not seized by the Hartree-Fock ansatz) plays a more prominent role. We show that these two different viewpoints on electron correlation are closely related. The key ingredient turns out to be the energy gap within the symmetry-adapted subspace. We then use a few-site Hubbard model and the stretched H$_2$ to illustrate this connection and to show how the corresponding measures of correlation compare., Comment: 6 pages, 3 figures

The role of the generalized Pauli constraints (GPCs) in higher spatial dimensions and by incorporating spin degrees of freedom is systematically explored for a system of interacting fermions confined by a harmonic trap. Physical relevance of the GPCs is confirmed by analytical means for the ground state in the regime of weak couplings by finding its vector of natural occupation numbers close to the boundary of the allowed region. Such quasipinning is found to become weaker in the intermediate and strong coupling regime. The study of crossovers between different spatial dimensions by detuning the harmonic trap frequencies suggests that quasipinning is essentially an effect for systems with reduced spatial dimensionality. In addition, we find that quasipinning becomes stronger by increasing the degree of spin-polarization. Consequently, the number of states available around the Fermi level plays a key role for the occurrence of quasipinning. This suggests that quasipinning emerges from the conflict between energy minimization and fermionic exchange symmetry., Comment: published version

Analytical evidence for the physical relevance of generalized Pauli constraints (GPCs) has recently been provided in [PRL 110, 040404]: Natural occupation numbers $\vec{\lambda}\equiv (\lambda_i)$ of the ground state of a model system in the regime of weak couplings $\kappa$ of three spinless fermions in one spatial dimension were found extremely close, in a distance $D_{min}\sim \kappa^8$ to the boundary of the allowed region. We provide a self-contained and complete study of this quasipinning phenomenon. In particular, we develop tools for its systematic exploration and quantification. We confirm that quasipinning in one dimension occurs also for larger particle numbers and extends to intermediate coupling strengths, but vanishes for very strong couplings. We further explore the non-triviality of our findings by comparing quasipinning by GPCs to potential quasipinning by the less restrictive Pauli exclusion principle constraints. This allows us to eventually confirm the significance of GPCs beyond Pauli's exclusion principle.

Pauli's exclusion principle has a strong impact on the properties of most fermionic quantum systems. Remarkably, the fermionic exchange symmetry implies further constraints on the one-particle picture. By exploiting those generalized Pauli constraints we derive a measure which quantifies the influence of the exchange symmetry beyond Pauli's exclusion principle. It is based on a geometric hierarchy induced by the exclusion principle constraints. We provide a proof of principle by applying our measure to a simple model. In that way, we conclusively confirm the physical relevance of the generalized Pauli constraints and show that the fermionic exchange symmetry can have an influence on the one-particle picture beyond Pauli's exclusion principle. Our findings provide a new perspective on fermionic multipartite correlation since our measure allows one to distinguish between static and dynamic correlations., Comment: title has been changed; very close to published version

For $N$ spin-polarized fermions with harmonic pair interactions in a $1$-dimensional trap an odd-even effect is found. The spectrum of the $1$-particle reduced density matrix of the system's ground state differs qualitatively for $N$ odd and $N$ even. This effect does only occur for strong attractive and repulsive interactions. Since it does not exists for bosons, it must originate from the repulsive nature implied by the fermionic exchange statistics. In contrast to the spectrum, the $1$-particle density and correlation function for strong attractive interactions do not show any sensitivity on the number parity. This also suggests that reduced-density-matrix-functional theory has a more subtle $N$-dependency than density functional theory., Comment: published version

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., Comment: PhD thesis, ETH Zurich. Section 2.2 has some overlap with arXiv:1404.1085, section 4.2 is based on arXiv:1210.5531 and arXiv:1307.6858, section 4.3 is partly based on arXiv:1506.08833

Fermionic natural occupation numbers do not only obey Pauli's exclusion principle, but are even further restricted by so-called generalized Pauli constraints. Such restrictions are particularly relevant whenever they are saturated by given natural occupation numbers $\vec{\lambda}=(\lambda_i)$. For few-site Hubbard models we explore the occurrence of this pinning effect. By varying the on-site interaction $U$ for the fermions we find sharp transitions from pinning of $\vec{\lambda}$ to the boundary of the allowed region to nonpinning. We analyze the origin of this phenomenon which turns out be either a crossing of natural occupation numbers $\lambda_{i}(U), \lambda_{i+1}(U)$ or a crossing of $N$-particle energies. Furthermore, we emphasize the relevance of symmetries for the occurrence of pinning. Based on recent progress in the field of ultracold atoms our findings suggest an experimental set-up for the realization of the pinning effect., Comment: published version

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 $|\Psi_N\rangle$ simplifies due to a selection rule. We show analytically and numerically for the most relevant settings that this rule is stable for NON close to the boundary, if the NON are non-degenerate. 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 $|\Psi_N\rangle$, its entanglement properties and correlations from 1-particle information. Our finding also provides the basis for a generalized Hartree-Fock method by a variational ansatz determined by the selection rule.

For states of quantum systems of $N$ particles with harmonic interactions we prove that each reduced density matrix $\rho$ obeys a duality condition. This condition implies duality relations for the eigenvalues $\lambda_k$ of $\rho$ and relates a harmonic model with length scales $l_1,l_2, \ldots, l_N $ with another one with inverse lengths $1/l_1, 1/l_2,\ldots, 1/l_N$. Entanglement entropies and correlation functions inherit duality from $\rho$. Self-duality can only occur for noninteracting particles in an isotropic harmonic trap.

The question of whether given density operators for subsystems of a multipartite quantum system are compatible to one common total density operator is known as the quantum marginal problem. We briefly review the solution of a subclass of such problems found just recently. In particular, this provides the solution of the $1$-body $N$-representability problem. Its solution, the so-called generalized Pauli constraints, restrict the set of mathematically possible fermionic occupation numbers significantly, and strengthens Pauli's exclusion principle. Moreover, we review the study of a concrete physical model of interacting fermions confined to a harmonic trap. There, we found occupation numbers close, but not exactly on the boundary of the allowed region. This new effect of quasipinning is physically relevant since it corresponds to a simplified structure of the corresponding $N$-fermion quantum state., Comment: 12 pages, contribution to the Proceedings of the Conference QMath 12 held in Berlin in September 2013

For a quantum system of N identical, harmonically interacting particles in a one-dimensional harmonic trap we calculate for the bosonic and fermionic ground state the corresponding 1-particle reduced density operator $\rho_1$ analytically. In case of bosons $\rho_1$ is a Gibbs state for an effective harmonic oscillator. Hence the natural orbitals are Hermite functions and their occupation numbers obey a Boltzmann distribution. Intriguingly, for fermions with not too large couplings the natural orbitals coincide up to just a very small error with the bosonic ones. In case of strong coupling this still holds qualitatively. Moreover, the decay of the decreasingly ordered fermionic natural occupation numbers is given by the bosonic one, but modified by an algebraic prefactor. Significant differences to bosons occur only for the largest occupation numbers. After all the "discontinuity" at the "Fermi level" decreases with increasing coupling strength but remains well pronounced even for strong interaction.

The Pauli exclusion principle is a constraint on the natural occupation numbers of fermionic states. It has been suspected since at least the 1970's, and only proved very recently, that there is a multitude of further constraints on these numbers, generalizing the Pauli principle. Here, we provide the first analytic analysis of the physical relevance of these constraints. We compute the natural occupation numbers for the ground states of a family of interacting fermions in a harmonic potential. Intriguingly, we find that the occupation numbers are almost, but not exactly, pinned to the boundary of the allowed region (quasi-pinned). The result suggests that the physics behind the phenomenon is richer than previously appreciated. In particular, it shows that for some models, the generalized Pauli constraints play a role for the ground state, even though they do not limit the ground-state energy. Our findings suggest a generalization of the Hartree-Fock approximation.