Superatom-assembly induced transition from insulator to semiconductor: A theoretical study
Source abstract
Abstract
Assembly is an effective way to realize the functionalization potential of boron-based superatoms. Here we study the interaction between typical boron-based B40 superatoms using the density functional theory. Our results reveal that different oligomers constructed by modulating the arrangement of two B40 superatoms still retain some of the superatomic properties associated with their monomeric form despite possessing different electronic structures. While the inner shell superatomic orbitals maintain their electronic localization, the valence shell superatomic orbitals cannot maintain their original shape due to bonding and antibonding hybridization. Furthermore, the decreasing of band gap means that the B40 oligomers could achieve a transformation from insulators to semiconductors. The decreased band gap is possibly due to the disappearance of the superatomic orbitals with the principal quantum number of two. Our findings highlight that superatom–superatom interactions could induce synergy effects that differ from their monomers. Therefore, this research will aid in the development of new materials and devices that are constructed from superatoms.
Source: openaire · Quality: candidate unverified · Source record ↗
Research context
OpenAlex topics: MXene and MAX Phase Materials · 2D Materials and Applications · Nanocluster Synthesis and Applications
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
References (43)
Show source-provided references
1. Kalsin AM, Fialkowski M, Paszewski M, et al. Electrostatic selfassembly of binary nanoparticle crystals with a diamond-like lattice. Science, 2006, 312: 420–42410.1126/science.1125124 ↗
2. Sharma J, Chhabra R, Cheng A, et al. Control of self-assembly of DNA tubules through integration of gold nanoparticles. Science, 2009, 323: 112–11610.1126/science.1165831 ↗
3. Shevchenko EV, Talapin DV, Kotov NA, et al. Structural diversity in binary nanoparticle superlattices. Nature, 2006, 439: 55–5910.1038/nature04414 ↗
4. Daniel MC, Astruc D. Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev, 2004, 104: 293–34610.1021/cr030698+ ↗
5. Claridge SA, Castleman Jr. AW, Khanna SN, et al. Cluster-assembled materials. ACS Nano, 2009, 3: 244–255
6. Qian M, Reber AC, Ugrinov A, et al. Cluster-assembled materials: toward nanomaterials with precise control over properties. ACS Nano, 2010, 4: 235–24010.1021/nn9010297 ↗
7. Zhang S, Zhang Y, Huang S, et al. Theoretical investigation of growth, stability, and electronic properties of beaded ZnO nanoclusters. J Mater Chem, 2011, 21: 1690510.1039/c1jm12061a ↗
8. Zhang S, Zhang Y, Huang S, et al. Theoretical investigations of spsp2 hybridized zero-dimensional fullerenynes. Nanoscale, 2012, 4: 2839–284210.1039/c2nr30299c ↗
9. Roy X, Lee CH, Crowther AC, et al. Nanoscale atoms in solid-state chemistry. Science, 2013, 341: 157–16010.1126/science.1236259 ↗
10. Krätschmer W, Lamb LD, Fostiropoulos K, et al. Solid C60: a new form of carbon. Nature, 1990, 347: 354–35810.1038/347354a0 ↗
11. Liu F, Mostoller M, Kaplan T, et al. Evidence for a new class of solids. First-principles study of K(Al13). Chem Phys Lett, 1996, 248: 213–21710.1016/0009-2614(95)01339-3 ↗
12. Reber AC, Khanna SN, Castleman AW. Superatom compounds, clusters, and assemblies: ultra alkali motifs and architectures. J Am Chem Soc, 2007, 129: 10189–1019410.1021/ja071647n ↗
13. Khanna SN, Jena P. Assembling crystals from clusters. Phys Rev Lett, 1992, 69: 1664–166710.1103/PhysRevLett.69.1664 ↗
14. Castleman AW, Khanna SN, Sen A, et al. From designer clusters to synthetic crystalline nanoassemblies. Nano Lett, 2007, 7: 2734–274110.1021/nl071224j ↗
15. Yang H, Wang Y, Huang H, et al. All-thiol-stabilized Ag44 and Au12Ag32 nanoparticles with single-crystal structures. Nat Commun, 2013, 4: 242210.1038/ncomms3422 ↗
16. Champsaur AM, Yu J, Roy X, et al. Two-dimensional nanosheets from redox-active superatoms. ACS Cent Sci, 2017, 3: 1050–105510.1021/acscentsci.7b00328 ↗
17. Wang J, Yu T, Gao Y, et al. All-boron fullerene B40: a superatomic structure. Sci China Mater, 2017, 60: 1264–126810.1007/s40843-017-9123-8 ↗
18. Yu T, Gao Y, Xu D, et al. Actinide endohedral boron clusters: A closed-shell electronic structure of U@B40. Nano Res, 2018, 11: 354–35910.1007/s12274-017-1637-9 ↗
19. Zhai HJ, Zhao YF, Li WL, et al. Observation of an all-boron fullerene. Nat Chem, 2014, 6: 727–73110.1038/nchem.1999 ↗
20. Jin P, Hou Q, Tang C, et al. Computational investigation on the endohedral borofullerenes M@B40 (M = Sc, Y, La). Theor Chem Acc, 2015, 134: 1310.1007/s00214-014-1612-4 ↗
21. Bai H, Chen Q, Zhai HJ, et al. Endohedral and exohedral metalloborospherenes: M@B40 (M=Ca, Sr) and M&B40 (M=Be, Mg). Angew Chem Int Ed, 2015, 54: 941–94510.1002/anie.201408738 ↗
22. Fa W, Chen S, Pande S, et al. Stability of metal-encapsulating boron fullerene B40. J Phys Chem A, 2015, 119: 11208–1121410.1021/acs.jpca.5b07173 ↗
23. Dong H, Lin B, Gilmore K, et al. B40 fullerene: An efficient material for CO2 capture, storage and separation. Curr Appl Phys, 2015, 15: 1084–108910.1016/j.cap.2015.06.008 ↗
24. Gao G, Ma F, Jiao Y, et al. Modelling CO2 adsorption and separation on experimentally-realized B40 fullerene. Comput Mater Sci, 2015, 108: 38–4110.1016/j.commatsci.2015.06.005 ↗
25. Dong H, Hou T, Lee ST, et al. New Ti-decorated B40 fullerene as a promising hydrogen storage material. Sci Rep, 2015, 5: 995210.1038/srep09952 ↗
26. Lin B, Dong H, Du C, et al. B40 fullerene as a highly sensitive molecular device for NH3 detection at low bias: a first-principles study. Nanotechnology, 2016, 27: 07550110.1088/0957-4484/27/7/075501 ↗
27. Yang Z, Ji YL, Lan G, et al. Design molecular rectifier and photodetector with all-boron fullerene. Solid State Commun, 2015, 217: 38–4210.1016/j.ssc.2015.05.013 ↗
28. Shakerzadeh E, Biglari Z, Tahmasebi E. M@B40 (M = Li, Na, K) serving as a potential promising novel NLO nanomaterial. Chem Phys Lett, 2016, 654: 76–8010.1016/j.cplett.2016.05.014 ↗
29. Li Z, Yu G, Zhang X, et al. Bonding the superalkali M3O (M = Li and K): An effective strategy to improve the electronic and nonlinear optical properties of the inorganic B40 nanocage. Physica ELow-dimensional Syst Nanostruct, 2017, 94: 204–21010.1016/j.physe.2017.08.011 ↗
30. Yang Y, Zhang Z, Penev ES, et al. B40 cluster stability, reactivity, and its planar structural precursor. Nanoscale, 2017, 9: 1805–181010.1039/C6NR09385J ↗
31. Zheludev NI. The road ahead for metamaterials. Science, 2010, 328: 582–58310.1126/science.1186756 ↗
32. Grimme S, Antony J, Ehrlich S, et al. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys, 2010, 132: 154104–15410410.1063/1.3382344 ↗
33. Adamo C, Barone V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J Chem Phys, 1999, 110: 6158–617010.1063/1.478522 ↗
34. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–386810.1103/PhysRevLett.77.3865 ↗
35. Hehre WJ, Ditchfield R, Pople JA. Self-consistent molecular orbital methods. XII. Further extensions of Gaussian-type basis sets for use in molecular orbital studies of organic molecules. J Chem Phys, 1972, 56: 2257–2261
36. He R, Zeng XC. Electronic structures and electronic spectra of allboron fullerene B40. Chem Commun, 2015, 51: 3185–318810.1039/C4CC09151E ↗
37. Frisch MJ, Trucks GW, Schlegel HB, et al. Gaussian 09, revision d.01. 2013
38. Morokuma K. Molecular orbital studies of hydrogen bonds. III. C=O···H–O hydrogen bond in H2CO···H2O and H2CO···2H2O. J Chem Phys, 1971, 55: 1236–1244
39. Ziegler T, Rauk A. On the calculation of bonding energies by the Hartree Fock Slater method. Theoret Chim Acta, 1977, 46: 1–1010.1007/BF02401406 ↗
40. te Velde G, Bickelhaupt FM, Baerends EJ, et al. Chemistry with ADF. J Comput Chem, 2001, 22: 931–96710.1002/jcc.1056 ↗
41. Delley B. From molecules to solids with the DMol3 approach. J Chem Phys, 2000, 113: 7756–776410.1063/1.1316015 ↗
42. Kurakevych OO, Solozhenko VL. Rhombohedral boron subnitride, B13N2, by X-ray powder diffraction. Acta Crystlogr C Cryst Struct Commun, 2007, 63: i80–i8210.1107/S0108270107037353 ↗
43. Beu TA, Onoe J, Hida A. First-principles calculations of the electronic structure of one-dimensional C60 polymers. Phys Rev B, 2005, 72: 15541610.1103/PhysRevB.72.155416 ↗