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. 2021 Jun 17;6(25):16612-16622.
doi: 10.1021/acsomega.1c02016. eCollection 2021 Jun 29.

Role of Dispersion Interactions in Endohedral TM@(ZnS)12 Structures

Elisa Jimenez-Izal  1   2 , Iker Ortiz de Luzuriaga  3 , Eloy Ramos-Cordoba  1 , Jon M Matxain  1
Affiliations

Role of Dispersion Interactions in Endohedral TM@(ZnS)12 Structures

Elisa Jimenez-Izal et al. ACS Omega. .

Abstract

II-VI semiconducting materials are gaining attention due to their optoelectronic properties. Moreover, the addition of transition metals, TMs, might give them magnetic properties. The location and distance of the TM are crucial in determining such magnetic properties. In this work, we focus on small hollow (ZnS)12 nanoclusters doped with TMs. Because (ZnS)12 is a cage-like spheroid, the cavity inside the structure allows for the design of endohedral compounds resembling those of C60. Previous studies theoretically predicted that the first-row TM(ZnS)12 endohedral compounds were thermodynamically unstable compared to the surface compounds, where the TM atom is located at the surface of the cluster. The transition states connecting both structure families were calculated, and the estimated lifetimes of these compounds were predicted to be markedly small. However, in such works dispersion effects were not taken into account. Here, in order to check for the influence of dispersion on the possible stabilization of the desired TM(ZnS)12 endohedrally doped clusters, several functionals are tested and compare to MP2. It is found that the dispersion effects play a very important role in determining the location of the metals, especially in those TMs with the 4s3d shell half-filled or completely filled. In addition, a complete family of TM doped (ZnS)12 nanoclusters is explored using ab initio molecular dynamics simulations and local minima optimizations that could guide the experimental synthesis of such compounds. From the magnetic point of view, the Cr(7S)@(ZnS)12 compound is the most interesting case, since the endohedral isomer is predicted to be the global minimum. Moreover, molecular dynamics simulations show that when the Cr atom is located at the surface of the cluster, it spontaneously migrates toward the center of the cavity at room temperature.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Figure 1
Figure 1
General picture for TM@(ZnS)12 structures, where surface compounds are more stable than their endohedral counterparts.
Figure 2
Figure 2
NCI analysis of TM doped (ZnS)12 nanoclusters. RDG isosurface with an isovalue of 0.3 au.
Figure 3
Figure 3
Quantum molecular dynamics results for 7Cr(ZnS)12 structures. Total energies and the trajectory of the 7Cr along the simulation time (top) for the ENDO structure and (bottom) for the SURFACE structure. On the left, total energies are depicted vs simulation steps. Each step is 300 au.
Figure 4
Figure 4
Examples of the seven structure family isomers detected in the MD simulations.
Figure 5
Figure 5
Energy profiles of all the TM doped (ZnS)12, in which the TM has either 4s1d5 (above) or 4s2d5 (below) electronic structure.
Figure 6
Figure 6
Most stable high- and low-spin structures for all the TM doped (ZnS)12, in which the TMs have either 4s1d5 or 4s2d5 electronic structure.
Figure 7
Figure 7
Energy profiles of all the TM doped (ZnS)12, in which the TMs have either 4s1d10 (top) or 4s2d10 (bottom) electronic structure.
Figure 8
Figure 8
Most stable high- and low-spin structures for all the considered TM doped (ZnS)12, in which the TMs have either 4s1d10 or 4s2d10 electronic structure.
See this image and copyright information in PMC

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