Structures, relative stabilities, and electronic properties of potassium clusters Kn (13⩽n⩽80)

Aguado, Andrés

doi:10.1016/j.comptc.2013.06.040

Cited by 7 publications

(5 citation statements)

References 78 publications

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“…Photoelectron spectrometry has obtained strong evidence of an icosahedron-like structure for cationic alkali clusters, for example, Na 55 + , which was also supported by first-principles calculations for both cationic and neutral 55-atom nanoclusters. , Thus it is a direct example where the geometric packing for alkali cluster is correlated with its electronic structure, as described by the Jellium model. Recently, a density functional theory (DFT) study reported a magnetic feature for the Na 55 and K 55 nanoclusters, which was suggested as a preponderant property in the enhancement of the thermal stability of icosahedral Na 55 + nanoclusters . On the other side, for Cs 55 , the geometric packing plays a dominant role in the stability of the icosahedron structure, which is explained by atomic characteristics, such as smaller size of the Cs atoms, relativistic effects, and sd hybridization. − …”

Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

et al. 2016

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An atom-level ab initio understanding of the structural, energetic, and electronic properties of nanoclusters with diameter size from 1 to 2 nm figures as a prerequisite to foster their potential technological applications. However, because of several challenges such as the identification of ground-state structures by experimental and theoretical techniques, our understanding is still far from satisfactory, and further studies are required. We report a systematic ab initio investigation of the 55-atom metal nanoclusters, (M 55 ), including alkaline, transitional, and post-transitional metals, that is, a total of 42 systems. Our calculations are based on all-electron density functional theory within the Perdew−Burke−Ernzerhof (PBE) functional combined with van der Waals (vdW) correction, spin−orbit coupling (SOC) for the valence states. Furthermore, we also investigated the role of the localization of the d states by using the PBE+U functional. We found a strong preference for the putative PBE global-minimum configurations for the compact Mackay icosahedron structure, namely, 16 systems (Na, Mg, K, Sc, Ti, Co, Ni, Cu, Rb, Y, Ag, Cs, Lu, Hf, Re, Hg), while several systems adopt alternative compact structures such as 6 polytetrahedron (Ca, Mn, Fe, Sr, Ba, Tl) and 10 structures derived from crystalline face-centered cubic and hexagonal close-packed (HCP) fragments (Cr, Nb, Mo, Tc, Ru, Rh, Pd, Ta, W, Os). However, the 10 remaining systems adopt less compact structures based on the distorted reduced-core structure (V, Zn, Zr, Cd, In, Pt, Au), tetrahedral-like (Al, Ga), and one HCP wheel-type (Ir) structure. The binding energy shows a quasi-parabolic behavior as a function of the atomic number, and hence the occupation of the bonding and antibonding states defines the main trends (binding energy, equilibrium bond lengths, etc.). On average, the binding energy of the M 55 systems represents 79% of the cohesive energy of the respective bulk systems. The addition of the vdW correction changes the putative global-minimum configurations (pGMCs) for selected cases, in particular, for post-transitional metal systems. As expected, the PBE+U functional increases the total magnetic moment, which can be explained by the increased localization of the d states, which also contributed to increase the number of atoms in the core region (increase coordination) of the pGMCs. In contrast with the effects induced by the vdW correction and localization of the d states, the addition of the SOC coupling cannot change the lowest energy configurations, but it affects the electronic properties, as expected from previous calculations for 13-atom clusters.

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Section: Introductionmentioning

confidence: 99%

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

et al. 2016

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“…[53]. K n clusters behave in a similar manner [22]. K 54 has a quintet ground state in DFT corrected for dispersion interactions; K 55 and K 71 are quartets.…”

Section: Validity Of Hund's Rule In Clustersmentioning

confidence: 89%

“…At larger sizes, things could be different. The geometric packing effects become more important at larger sizes, and the role of electronic shell structure in determining the stable clusters diminishes [22,53]. In such a regime, even alkali clusters may have high-spin ground states as the crystalfield splitting due to JT distortion is small.…”

Section: Validity Of Hund's Rule In Clustersmentioning

confidence: 97%

“…Although I started the discussion on simple metal clusters with spherical shell models, not all clusters are 'spherical'. Only when highsymmetry structures happen to be ground states, either due to filled electronic shells or complete geometric shells, the clusters are found to be spherical as measured by the so-called Hill-Wheeler parameter [1,21,22]. Clusters having partially filled shells usually have distortions from a perfectly spherical shape.…”

Section: Introductionmentioning

confidence: 98%

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Magnetism in Simple Metal and 4d Transition Metal Clusters

Sen

2016

J Clust Sci

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In this review article I discuss two aspects of magnetism in small metal clusters. The first question discussed is whether simple metal clusters, that obey electronic shell models and mimic properties of elemental atoms, also obey Hund's rule of maximum spin multiplicity. The second question is whether small clusters of 4d transition metal atoms, that are non-magnetic in the bulk, have magnetic ground states. The question arises because calculations showed that small V clusters are magnetic although the bulk metal is not. We discuss known results on Rh clusters in detail to show that small clusters are generally magnetic, but it is difficult to unequivocally identify the ground state due to the presence of many isomers and spin states that are very close in energy.

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“…Much theoretical and experimental work was reported on properties of pure potassium cluster species . Also, many heterogeneous clusters of potassium, among them potassium iodide clusters, are experimentally and theoretically investigated.…”

Section: Introductionmentioning

confidence: 99%

Theoretical and experimental investigation of geometry and stability of small potassium‐iodide K_nI (n = 2–6) clusters

Milovanovic

Milovanović

Veličković

et al. 2019

Int J of Quantum Chemistry

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Small heterogeneous potassium‐iodide clusters are investigated by means of ab initio electronic structural methods together with experimental production and detection in mass spectrometry. Experiments were done by using Knudsen cell mass spectrometry (KCMS) modification method, which provided simultaneous generating of all KnI0,+1 (n = 2–6) clusters at once. Clusters with more than two potassium atoms are produced for the first time. The lowest lying isomers of those KnI0,+1 (n = 2–6) clusters were found by using a random‐kick procedure. The best description of growth of these clusters is the addition of one potassium atom to a smaller‐neighbor cluster. Subsequently, stability of these species was examined. In spite of general trend of decreasing of binding energies, the closed‐shell species have slightly larger stability with respect to the open‐shell species. Alternation of dissociation energies between closed‐shell and open‐shell clusters is presented. Experimental setup also allows determination of ionization energies of clusters: the obtained values are in the range of 3.46–3.98 eV, which classify these clusters as “superalkali.” For closed‐shell clusters, the theoretical adiabatic ionization energies are close to experimental values, whereas in the case of open‐shell clusters, the vertical ionization energies are those that are close to experimental values.

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Structures, relative stabilities, and electronic properties of potassium clusters Kn (13⩽n⩽80)

Cited by 7 publications

References 78 publications

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

Magnetism in Simple Metal and 4d Transition Metal Clusters

Theoretical and experimental investigation of geometry and stability of small potassium‐iodide K_nI (n = 2–6) clusters

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Structures, relative stabilities, and electronic properties of potassium clusters Kn (13⩽n⩽80)

Cited by 7 publications

References 78 publications

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

Theoretical Study of the Structural, Energetic, and Electronic Properties of 55-Atom Metal Nanoclusters: A DFT Investigation within van der Waals Corrections, Spin–Orbit Coupling, and PBE+U of 42 Metal Systems

Magnetism in Simple Metal and 4d Transition Metal Clusters

Theoretical and experimental investigation of geometry and stability of small potassium‐iodide KnI (n = 2–6) clusters

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Theoretical and experimental investigation of geometry and stability of small potassium‐iodide K_nI (n = 2–6) clusters