Classical and quantum orbital correlations in molecular electronic states

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.

Automated summary

The quantum superposition principle is widely used in describing the bonding phenomenon in quantum mechanics. It explains the emergence of delocalized molecular orbitals and provides a method for constructing accurate electronic wavefunctions. In composite systems, the existence of quantum superposition can result in nonclassical correlations, which are considered as a resource in quantum technologies. In this study, we analyze the electronic ground states of three prototypical molecules using the framework of fermionic information theory. By introducing the concept of orbital discord, we decompose the pairwise orbital correlations into their classical and quantum parts in the presence of superselection rules. We find that quantum orbital correlations can be stronger than classical orbital correlations, although this is not often the case. Moreover, quantum orbital correlations can still exist 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.