Theoretical Study On Intramolecular Interaction And Hund's Rule Of Superatoms

Superatoms not only show the electronic structure properties similar to atoms,but also have a rich variety of types.Changing the structure and conponents can regulate the properties,thus bringing the prospect of new materials and even devices.The premise of accessing to the application depends on understanding the superatomic intramolecular interactions and grasping the physical mechanism at the atomic level.In the relevant fundamental researches,the intramolecular interaction of systems with high angular momentum electrons is one of the difficulties.Its comprehension for superatomic intramolecular interactions is of great significance.In this paper,by exploring the relationship between superatomic intramolecular interaction and electronic structure,we formed the understanding on the electron structure of superatom,especially the decisive effect of electron occupation on the structure.Taksing that as a basic standpoint,we provided insights for the high magnetic origin of superatoms.Through the electron assignment of light-element superatoms obeying the Hund's rule,the high magnetic properties are realized,which provides a new path for the construction of magnetic units.The systems of actinium elements with high angular momentum 5f valence embedded in coin-metal clusters can present novel optical and magnetic properties.Thereinto,typical example is the Th@Au14 superatom formed embedded with thorium(Th)atom in a Au14 cage,which exhibits huge potential in Surface-enhanced Raman scattering(SERS).Accordingly,using quantitatively analytical energy decomposition analysis(EDA)method,we explored the effect of the electron occupations of Th atom and Au14 cage on their interaction.The results show that the interaction between Th atom and Au14 cage can exhibite different properties under different electron occupation(that is,different electron division),suggesting that the two fragments are combined with different bonding types.It was found that,in the same electron state,the interaction between fragments with high-Z elements brings about obvious differences under different electron occupation types.During the bonding of the fragments,various electron occupation types can change the instantaneous interaction energy composition,such as electron relaxation,charge transfer and polarization.This illustrates the importance of partition fragment for theoretical researches,and benifits the resolution of fundamental issues in the regulation of intramolecular interactions by changing the electronic structure.Based on important insights from the above research,the high-stability,highmagnetism superatom composed entirely of light atoms boron(B)and nitrogen(N)were obtained by removing half electrons from the outermost electronic orbitals,which belongs to the 2F shell of the superatom B16N16.The ground state is the highest spin state with seven unpaired spin-up valence electrons,and the magnetic moment reaches 7?B.The magnetism is dictated entirely by the Hund's maximum spin rule.Importantly,the chemical and structural stabilities of the superatoms are not jeopardized by its high spins.Compared with most of the magnetic superatoms determined by the alkali metal or alkaline earth metal clusters containing d and f electron elements,it shows great advantages in structure and energy stability.The discovery not only provides prospects for simulating the elements with high angular momentum electorns,but also brings opportunities to achieve high magnetic properties beyond natural atoms.Further,it also provides a new light weight,high magnetic,and high magnetic properties based on superatoms.The synthesis of high-stability materials has laid an important foundation.In conclusion,this paper explores the relationship between electronic structures and intramolecular interaction within superatom formed by high-Z elements.On this basis,realizes the construction of light-element superatoms with high angular momentum,high magnetic state constrained by the Hund's rule,which brings important prospects to the design of low-cost,high-stability artificial units.