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arXiv:2107.13992 · New Journal of Physics

Classical and quantum orbital correlations in molecular electronic states

Onur Pusuluk, Mahir H. Yeşiller, Gökhan Torun, Özgür Esat Müstecaplıoğlu, Ersin Yurtsever, Vlatko Vedral

Published Sep 20, 2022• 6 citations
arXivHTMLPDF

Abstract

Abstract The quantum superposition principle has been extensively utilized in the quantum mechanical description of bonding phenomenon. It explains the emergence of delocalized molecular orbitals and provides a recipe for the construction of near-exact electronic wavefunctions. On the other hand, its existence in composite systems may give rise to nonclassical correlations that are regarded as a resource in quantum technologies. Here, we approach the electronic ground states of three prototypical molecules in the light of the framework set by fermionic information theory. By introducing the notion of orbital discord, we additively decompose the pairwise orbital correlations into their classical and quantum parts in the presence of superselection rules. We observe that quantum orbital correlations can be stronger than classical orbital correlations though not often. Moreover, quantum orbital correlations can survive even in the absence of orbital entanglement depending on the symmetries of the constituent orbitals. Finally, we demonstrate that orbital entanglement would be underestimated if the orbital density matrices were treated as qubit states.

DOI
10.1088/1367-2630/ac932b

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Abstract The quantum superposition principle has been extensively utilized in the quantum mechanical description of bonding phenomenon. It explains the emergence of delocalized molecular orbitals and provides a recipe for the construction of near-exact electronic wavefunctions. On the other hand, its existence in composite systems may give rise to nonclassical correlations that are regarded as a resource in quantum technologies. Here, we approach the electronic ground states of three prototypical molecules in the light of the framework set by fermionic information theory. By introducing the notion of orbital discord, we additively decompose the pairwise orbital correlations into their classical and quantum parts in the presence of superselection rules. We observe that quantum orbital correlations can be stronger than classical orbital correlations though not often. Moreover, quantum orbital correlations can survive even in the absence of orbital entanglement depending on the symmetries of the constituent orbitals. Finally, we demonstrate that orbital entanglement would be underestimated if the orbital density matrices were treated as qubit states.
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Abstract The goal of the present work is to guide the development of quantum technologies in the context of fermionic systems. For this, we first elucidate the process of entanglement swapping in electron systems such as atoms, molecules or solid bodies. This demonstrates the significance of the number-parity superselection rule and highlights the relevance of localized few-orbital subsystems for quantum information processing tasks. Then, we explore and quantify the entanglement between localized orbitals in two systems, a tight-binding model of non-interacting electrons and the hydrogen ring. For this, we apply the first closed formula of a faithful entanglement measure, derived in (arXiv: 2207.03377 ) as an extension of the von Neumann entropy to genuinely correlated many-orbital systems. For both systems, long-distance entanglement is found at low and high densities η, whereas for medium densities, η ≈ 1 2 , practically only neighboring orbitals are entangled. The Coulomb interaction does not change the entanglement pattern qualitatively except for low and high densities where the entanglement increases as function of the distance between both orbitals.
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A simple expression to compute the quantum discord between two orbitals in fermion systems is derived using the parity superselection rule. As the correlation between orbitals depends on the basis chosen, we discuss a special orbital basis, the natural one. We show that quantum correlations between natural orbital pairs disappear when the pairing tensor is zero, i.e., the particle number symmetry is preserved. The Hartree-Fock orbitals within a Slater determinant state, Hartree-Fock-Bogoliubov quasiparticle orbitals in a quasiparticle vacuum, or the ground state of a Hamiltonian with particle symmetry and their corresponding natural orbitals are some relevant examples of natural bases and their corresponding states. Since natural orbitals have that special property, we seek the quantum discord in non-natural orbital bases. We analyze our findings in the context of the Lipkin-Meshkov-Glick and Agassi models.