Vikas Chauhan

Hund’s rule in superatoms with transition metal impurities

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund’s rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMgn clusters where TM is a 3d atom. The clusters exhibit Hund’s filling, opening the pathway to superatoms with magnetic shells.

Nature of Valence Transition and Spin Moment in AgnV+ Clusters

Evolution in the atomic structure, bonding characteristics, stability, and the spin magnetic moment of neutral and cationic AgnV clusters has been investigated using first-principles density functional approach with gradient corrected functional. It is shown that at small sizes, the V 4s states hybridize with Ag states to form 1S and 1P like superatomic orbitals, whereas the 3d states are localized on V giving the V atom an effective valence of 1 or 2. Starting from Ag8V(+), the V 3d states begin to participate in the bonding by hybridizing with the nearly free electron gas to form 1D superatomic orbitals increasing the V atom effective valence toward 5. For the cationic clusters, this changing valence results in three shell closures that lead to stable species. These occur for cationic clusters containing 5, 7, and 14 Ag atoms. The first two stable species correspond to filled 1S and 1P shells in two and three dimensions with a valence of 2 for V, whereas the closure at 14 Ag atoms correspond to filled 1S, 1P, and 1D shells with V site exhibiting a valence of 5. The transition from filled 1S and 1P shells to filled 1S, 1P, and 1D shells is confirmed by a quenching of the spin magnetic moment. The theoretical findings are consistent with the observed drops in intensity in the mass spectrum of AgnV(+) clusters after 5, 7, and 14 Ag atoms.

Ni9Te6(PEt3)8C60 Is a Superatomic Superalkali Superparamagnetic Cluster Assembled Material (S3-CAM)

First-principles theoretical studies enable an electronic and magnetic characterization of the recently synthesized Ni9Te6(PEt3)8C60 ionic material consisting of Ni9Te6(PEt3)8 superatoms and C60. The PEt3 ligands are shown to create an internal coulomb well that lifts the quantum states of the Ni9Te6 cluster, lowering its ionization potential to 3.39 eV thus creating a superalkali motif. The metallic core has a spin magnetic moment of 5.3 μB in agreement with experiment. The clusters are marked by low magnetic anisotropy energy (MAE) of 2.72 meV and a larger intra-exchange coupling exceeding 0.2 eV, indicating that the observed paramagnetic behavior around 10K is due to superparamagnetic relaxations. The magnetic motifs separated by C60 experience a weak superexchange that stabilizes a ferromagnetic ground state as observed around 2 K. The calculated MAE is sensitive to the charged state that could account for the observed change in magnetic transition temperature with size of the ligands or anion.

Metal Chalcogenide Clusters with Closed Electronic Shells and the Electronic Properties of Alkalis and Halogens

Clusters with filled electronic shells and a large gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are generally energetically and chemically stable. Enabling clusters to become electron donors with low ionization energies or electron acceptors with high electron affinities usually requires changing the valence electron count. Here we demonstrate that a metal cluster may be transformed from an electron donor to an acceptor by exchanging ligands while the neutral form of the clusters has closed electronic shells. Our studies on Co6Te8(PEt3)m(CO)n (m + n = 6) clusters show that Co6Te8(PEt3)6 has a closed electronic shell and a low ionization energy of 4.74 eV, and the successive replacement of PEt3 by CO ligands ends with Co6Te8(CO)6 exhibiting halogen-like behavior. Both the low ionization energy Co6Te8(PEt3)6 and high electron affinity Co6Te8(CO)6 have closed electronic shells marked by high HOMO-LUMO gaps of 1.24 and 1.39 eV, respectively. Further, the clusters with an even number of ligands favor a symmetrical placement of ligands around the metal core.

Structural, electronic and magnetic properties of binary transition metal aluminum clusters: absence of electronic shell structure

Single Cr, Mn, Fe, Co and Ni doped Al clusters having up to 12 Al atoms are studied using density functional methods. The global minima of structure for all the clusters are identified, and their relative stability and electronic and magnetic properties are studied. FeAl4 and CoAl3 are found to have enhanced stability and aromatic behavior. In contrast to binary transition metal alkali and transition metal alkaline earth clusters, spherical shell models cannot describe the electronic structure of transition metal aluminum clusters.

Symmetry and magnetism in Ni9Te6 clusters ligated by CO or phosphine ligands

The removal of a single ligand from the magnetic Ni9Te6(L)8 (L = P(CH3)3, CO) clusters is found to quench the magnetic moment. The reduction in magnetic moment is caused by a geometric deformation of the Ni9Te6 core that breaks the octahedral symmetry of the cluster. This effect is observed in both the CO and phosphine based ligands. The octahedral symmetry bare cluster is also found to have a large magnetic moment. These results highlight the dilemma faced by magnetic ligand protected clusters whose symmetry has been broken: whether to break the spin symmetry as in Hunds rules or to break the spatial symmetry as in the Jahn-Teller effect. The spatial symmetry breaking is found to be an oblate distortion that forms additional Ni-Te bonds resulting in the enhanced stability of the cluster.

Strong lowering of ionization energy of metallic clusters by organic ligands without changing shell filling

Alkali atoms have unusually low ionization energies because their electronic structures have an excess electron beyond that of a filled electronic shell. Quantum states in metallic clusters are grouped into shells similar to those in atoms, and clusters with an excess electron beyond a closed electronic may also exhibit alkali character. This approach based on shell-filling is the way alkali species are formed as explained by the periodic table. We demonstrate that the ionization energy of metallic clusters with both filled and unfilled electronic shells can be substantially lowered by attaching ligands. The ligands form charge transfer complexes where the electronic spectrum is lifted via crystal field like effect. We demonstrate that the effect works for the weakly bound ligand, N-ethyl-2-pyrrolidone (EP = C6H11NO), and that the effect leads to a dramatic lowering of the ionization energy independent of the shell occupancy of the cluster.Metallic clusters with an excess electron beyond a closed shell have very low ionization energies, in analogy to alkali atoms. Here, the authors use select ligands to lower the ionization energy of metallic clusters without changing the number of valence electrons, introducing a route to alkali-like superatoms that is independent of the final shell occupancy.

Strong Effect of Organic Ligands on the Electronic Structure of Metal-Chalcogenide Clusters

It is shown that multiple ionization energies of metal-chalcogenide clusters can be substantially reduced by adding ligands that form charge transfer complexes. We demonstrate this intriguing phenomenon by considering metal-chalcogenide clusters including cases where a cluster has a filled electronic shell with a large gap between the occupied and unoccupied states reminiscent of stable species. The studies include a Co6Se8 core ligated with tri-ethylphosphine (PEt3) ligands forming a stable Co6Se8(PEt3)6 species. All of the ligated clusters have a first ionization energy in the range for alkali atoms and multiple ionization energies that are considerably lower than those for the non-ligated clusters. The change in electronic behavior upon ligation can be associated with a shift in the electronic spectrum via a crystal field like effect due to attaching ligands that form charge transfer complexes. We also show that metal-chalcogenide species can be programmed by proper ligand replacement to promote dimerization by first forming the Co6Se8(PEt3) n(CO)6- n ( n = 0-6) clusters where the CO ligands could be replaced by diisocyanide (CNC6H4NC) ligands. The diisocyanide ligand acts as a rigid linker between the metallic cores, enabling the formation of a Co6Se8(PEt3)5(CNC6H4NC)Co6Se8(PEt3)5 superatomic molecule (SM), and we examine the electronic and magnetic properties of the recently synthesized SM via studies on an analogous SM with smaller ligands.