Lithium-oxygen charge transfer interaction: a deformation density analysis study

Lithium and oxygen interaction plays a cornerstone role in lithium ion and lithium air batteries and lithium based technologies. In this way, oxidation and reduction of neutral and charged lithium is the key process in its application as power source and sustainable energies. Since both oxidation and reduction are based on charge transfer in molecular scale, they can be analyzed via electronic structure changes. Two types of fragmentations for charged complexes were suggested, in which the positive charge was located on either lithium or oxygen fragment. Deformation density analysis is a recently developed technique for identification of different intermolecular interactions in the context of quantum chemical language. In this analysis, the molecular orbitals of isolated fragments were employed to build non-interacting and anti-symmetrized fragments and the corresponding density matrices to find deformation density matrix of each one. In the present study, two types of deformation density including kinetic energy pressure and relaxation analyses were accomplished for lithium and oxygen interaction at B۳LYP/۶-۳۱۱+G* theoretical level. Electronic deformation orbitals responsible for charge transfer were identified with respect to their eigenvalues. The results showed how these two competed with each other in neutral and charged complexes with different fragmentations.

کلیدواژه ها:

Lithium ، Oxygen ، Deformation density ، Reduction ، Oxidation