Structural evolution and electronic properties of pure and semiconductor atom doped in clusters: In_n⁻, In_nSi⁻, and In_nGe⁻ (n = 3–16)

Abstract

The bonding and electronic properties of Inn−, InnSi−, and InnGe− (n = 3–16) clusters have been computationally investigated. An intensive global search for the ground‐state structures of these clusters were conducted using the genetic algorithm coupled with density functional theory (DFT). The ground‐state structures of these clusters have been identified through the comparison between simulated photoelectron spectra (PES) of the found lowest‐energy isomers and the experimentally measured ones. Doping semiconductor atom (Si or Ge) can significantly change the structures of the In clusters in most sizes, and the dopant prefers to be surrounded by In atoms. There are three structural motifs for InnX− (X = Si, Ge, n = 3–16), and the transition occurs at sizes n = 5 and 13. All InnSi− and InnGe− share the same configurations and similar electronic properties except for n = 8. Among all above studied clusters, In13− stands out with the largest vertical detachment energy (VDE), HOMO–LUMO gap, (Eb) and second order energy difference Δ2E due to its closed electronic shell of (1S)2(1P)6(1D)10(2S)2(1F)14(2P)6. Similarly, the neutral In12X (X = Si, Ge) clusters are also identified as superatoms but with electronic configuration of (1S)2(1P)6(2S)2(1D)10(1F)14(2P)6.

Cr2Gen− (n = 15–20) clusters with two Cr atoms exhibited antiferromagnetic coupling

“…Global searches were performed for the global minimum structures of Cr 2 Ge n À (n = 15-20) through a homemade genetic algorithm code combined with DFT calculations in ORCA 5.0.3 program. 37,38 The validity and efficiency of our genetic algorithm code have been demonstrated in our recent studies on TMSi 14-20 [39][40][41] TMGe 8-17 À (TM = Ti, Zr, Hf, V, Nb, Ta), 33 and In m X n À (m = 3-16, n = 0, 1; X = Si, Ge) 42 clusters. During the global search process, the PBE functional 43 with the 6-31 + G(d) 44,45 basis set was adopted for DFT calculations.…”

Antiferromagnetic Chromium-Doped Tin Clusters

“…To fully sample on their potential energy surfaces, more than 200, 1000, and 2000 configurations were generated for sizes n ≤ 10, 10 < n ≤ 15, and 15 < n ≤ 20, respectively. The validity and efficiency of our GA code can be demonstrated in our recent works on binary clusters including Cs/V/Cr/CrMn-doped Si n ( n ≤ 25), ,− TM-doped Ge 8–17 – (TM = Ti–Ta), , In 3–16 X – (X = Si, Ge), and pure Ge 4–30 – and Sn 21–35 – clusters. Moreover, the reported configurations of Cr 2 X 3–20 – (X = Si, Ge) − clusters are also considered as candidates.…”

“…Based on this, we conducted systematic theoretical investigations on the structural evolution, stabilities, and magnetic properties of Cr 2 -doped Sn clusters in the size range of x = 3−20 and found that all these neutral clusters are AFM except for the ferrimagnetic size 11 with a triplet state and all their monocharged states are ferrimagnetic. 20,27 In 3−16 X − (X = Si, Ge), 28 and pure Ge 4−30 − and 29 Sn 21−35 −30 clusters. Moreover, the reported configurations of Cr 2 X 3−20 − (X = Si, Ge) 17−20 clusters are also considered as candidates.…”

Theoretical investigation of the structural evolution, electronic and magnetic properties of TMSi n − (TM= Mo, W; n = 8-17) clusters

“…In order to obtain more structural and electronic information about TMSi n − clusters, we conducted a systematically theoretical investigations on the structural evolution, electronic and magnetic properties of [44][45][46] , TMGe 8 − 17 − (TM = Ti, Zr, Hf, V, Nb, Ta) 58 , and In n X m − (X = Si, Ge; m = 0, 1, n = 3-16) 59 clusters. The scheme of BP86 60, 61 functional with Karlsruhetype basis sets [62][63][64] has been proven to be suitable for the exploration the structural evolution and electronic properties of V-Si and Cr-Si clusters in our previous works 45,46 , rationally, it was also chosen for the calculations of TMSi n − (TM = Mo, W; n = 8-17) clusters.…”