Ab initiocalculation of the metal-insulator transition in lithium rings

Abstract

We study how the Mott metal-insulator transition (MIT) is affected when we have to deal with electrons with different angular momentum quantum numbers. For that purpose we apply ab-initio quantum-chemical methods to lithium rings in order to investigate the analogue of a MIT. By changing the interatomic distance we analyse the character of the many-body wavefunction and discuss the importance of the $s-p$ orbital quasi-degeneracy within the metallic regime. The charge gap (ionization potential minus electron affinity) shows a minimum and the static electric dipole polarizability has a pronounced maximum at a lattice constant where the character of the wavefunction changes from significant $p$ to essentially $s$-type. In addition, we examine rings with bond alternation in order to answer the question under which conditions a Peierls distortion occurs.