A Systemic Insight into Exohedral Actinides and Endohedral Borospherenes: An&Bm and An@Bn (An=U, Np, Pu; m = 28, 32, 34, 36, 38, 40; n = 36, 38, 40)
Abstract
:1. Introduction
2. Results
2.1. Exohedral Actinide Borospherenes
2.2. Actinide Endohedral Borospherenes
3. Computational Methods
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
- Boustani, I.; Quandt, A. Nanotubules of bare boron clusters: Ab initio and density functional study. Europhys. Lett. 1997, 39, 527–532. [Google Scholar] [CrossRef]
- Gindulytė, A.; Lipscomb, W.N.; Massa, L. Proposed boron nanotubes. Inorg. Chem. 1998, 37, 6544–6545. [Google Scholar] [CrossRef] [PubMed]
- Zhai, H.J.; Alexandrova, A.N.; Birch, K.A.; Boldyrev, A.I.; Wang, L.S. Hepta- and octacoordinate boron in molecular wheels of eight- and nine-atom boron clusters: Observation and confirmation. Angew. Chem. Int. Ed. 2003, 42, 6004–6008. [Google Scholar] [CrossRef] [PubMed]
- Piazza, Z.A.; Li, W.L.; Romanescu, C.; Sergeeva, A.P.; Wang, L.S.; Boldyrev, A.I. A photoelectron spectroscopy and ab initio study of B21−: Negatively charged boron clusters continue to be planar at 21. J. Chem. Phys. 2012, 136, 104310. [Google Scholar] [CrossRef]
- Li, W.L.; Pal, R.; Piazza, Z.A.; Zeng, X.C.; Wang, L.S. B27−: Appearance of the smallest planar boron cluster containing a hexagonal vacancy. J. Chem. Phys. 2015, 142, 204305. [Google Scholar] [CrossRef]
- Li, H.R.; Jian, T.; Li, W.L.; Miao, C.Q.; Wang, Y.J.; Chen, Q.; Wang, L.S.; Zhai, H.J.; Li, S.D. Competition between quasi-planar and cage-like structures in the B29− cluster: Photoelectron spectroscopy and ab initio calculations. Phys. Chem. Chem. Phys. 2016, 18, 29147–29155. [Google Scholar] [CrossRef]
- Luo, X.M.; Luo, X.M.; Jian, T.; Cheng, L.J.; Li, W.L.; Chen, Q.; Li, R.; Wang, L.S.; Jian, T.; Li, J.; et al. B26−: The smallest planar boron cluster with a hexagonal vacancy and a complicated potential landscape. Chem. Phys. Lett. 2017, 683, 336–341. [Google Scholar] [CrossRef]
- Klyukin, I.N.; Kolbunova, A.V.; Novikov, A.S.; Nelyubin, A.V.; Selivanov, N.A.; Bykov, A.Y.; Klyukina, A.A.; Zhdanov, A.P.; Zhizhin, K.Y.; Kuznetsov, N.T. Protonation of Borylated Carboxonium Derivative [2,6-B10H8O2CCH3]−: Theoretical and Experimental Investigation. Int. J. Mol. Sci. 2022, 23, 4190. [Google Scholar] [CrossRef]
- Hagemann, H.R.; Zhizhin, K.Y.; Kuznetsov, N.T. B-F bonding and reactivity analysis of mono- and perfluoro-substituted derivatives of closo-borate anions (6, 10, 12): A computational study. Polyhedron 2022, 211, 115559. [Google Scholar]
- Li, H.; Shao, N.; Shang, B.; Yuan, L.F.; Yang, J.; Zeng, X.C. Icosahedral B12-containing core-shell structures of B80. Chem. Commun. 2010, 46, 3878–3880. [Google Scholar] [CrossRef]
- Zhao, J.; Wang, L.; Li, F.; Chen, Z. B80 and other medium-sized boron clusters: Core-shell structures, not hollow cages. J. Phys. Chem. 2010, 114, 9969–9972. [Google Scholar] [CrossRef] [PubMed]
- Zhai, H.J.; Zhao, Y.F.; Li, W.L.; Chen, Q.; Bai, H.; Hu, H.S.; Wang, L.S.; Li, S.D.; Tian, W.J.; Lu, H.J.; et al. Observation of an all-boron fullerene. Nat. Chem. 2014, 6, 727–731. [Google Scholar] [CrossRef] [PubMed]
- Lv, J.; Wang, Y.; Zhu, L.; Ma, Y. B38: An all-boron fullerene analogue. Nanoscale 2014, 6, 11692–11696. [Google Scholar] [CrossRef] [PubMed]
- Wang, Y.J.; Zhao, Y.F.; Li, W.L.; Jian, T.; Chen, Q.; You, X.R.; Wang, L.S.; Ting, O.; Li, S.D.; Li, J.; et al. Observation and characterization of the smallest borospherene, B28− and B28. J. Chem. Phys. 2016, 144, 064307. [Google Scholar] [CrossRef]
- Liu, H.; Chen, Q.; Li, H.R.; Zhao, X.Y.; Tian, X.X.; Mu, Y.W.; Lu, H.G.; Li, S.D. Aromatic cage-like B34 and B35+: New axially chiral members of the borospherene family. Phys. Chem. Chem. Phys. 2018, 20, 15344–15349. [Google Scholar] [CrossRef] [PubMed]
- Pei, L.; Yan, M.; Zhao, X.Y.; Mu, Y.W.; Lu, H.G.; Wu, Y.B.; Li, S.D. Sea-shell-like B31+ and B32: Two new axially chiral members of the borospherene family. RSC Adv. 2020, 10, 10129–10133. [Google Scholar] [CrossRef]
- Yu, T.; Gao, Y.; Xu, D.; Wang, Z. Actinide endohedral boron clusters: A closed-shell electronic structure of U@B40. Nano Res. 2018, 11, 354–359. [Google Scholar] [CrossRef]
- Wang, C.; Bo, T.; Lan, J.; Wu, Q.; Chai, Z.; Gibsonc, J.K.; Shi, W. Ultrastable actinide endohedral borospherenes. Chem. Commun. 2018, 54, 2248–2251. [Google Scholar] [CrossRef]
- Du, J.G.; Jiang, G. Theoretical characterization of the endohedral metalloborospherenes M@B36 (M = Ti, Zr, Hf, Ce, Th, Pa+, U2+, Np3+, and Pu4+). J. Mol. Liq. 2020, 319, 114088. [Google Scholar] [CrossRef]
- Duan, M.; Li, P.; Zhao, H.; **e, F.; Ma, J. Organic Compounds of Actinyls: Systematic Computational Assessment of Structural and Topological Properties in [AnO2(C2O4)n](2n−2)− (An=U, Np, Pu, Am; n = 1−3) Complexes. Inorg. Chem. 2019, 58, 3425. [Google Scholar] [CrossRef]
- Cremer, D.; Kraka, E. Chemical bonds without bonding electron density-does the difference electron-density analysis suffice for a description of the chemical bond? Angew. Chem. Int. Ed. Engl. 1984, 23, 627. [Google Scholar] [CrossRef]
- Liu, Z.; Wang, X.; Lu, T.; Yuan, A.; Yan, X. Potential optical molecular switch: Lithium@ cyclo [18] carbon complex transforming between two stable configurations. Carbon 2022, 187, 78–85. [Google Scholar] [CrossRef]
- Perdew, J.P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865. [Google Scholar] [CrossRef] [PubMed]
- Neese, F. The ORCA program system. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2012, 2, 73–78. [Google Scholar] [CrossRef]
- Neese, F. Software update: The ORCA program system, version 4.0. Wiley Interdiscip. Rev. Comput. Mol. Sci. 2017, 8, 73–78. [Google Scholar] [CrossRef]
- Lenthe, E.V.; Baerends, E.J.; Snijders, J.G. Relativistic regular two-component Hamiltonians. J. Chem. Phys. 1993, 99, 4597. [Google Scholar] [CrossRef]
- Pantazis, D.A.; Neese, F. All-electron scalar relativistic basis sets for the actinides. J. Chem. Theory Comput. 2011, 7, 677–684. [Google Scholar] [CrossRef]
- Pritchard, B.P.; Altarawy, D.; Didier, B.; Gibson, T.D.; Windus, T.L. A New Basis Set Exchange: An Open, Up-to-date Resource for the Molecular Sciences Community. J. Chem. Inf. Model. 2019, 59, 4814–4820. [Google Scholar] [CrossRef]
- Goerigk, L.; Grimme, S. Efficient and Accurate Double-Hybrid-Meta-GGA Density Functionals-Evaluation with the Extended GMTKN30 Database for General Main Group Thermochemistry, Kinetics, and Noncovalent Interactions. J. Chem. Theory Comput. 2011, 7, 291. [Google Scholar] [CrossRef] [PubMed]
- Grimme, S.; Antony, J.; Ehrlich, S.; Krieq, H. 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. [Google Scholar] [CrossRef]
- Adamo, C.; Barone, V. Toward reliable density functional methods without adjustable parameters: The PBE0 model. J. Chem. Phys. 1999, 110, 6158. [Google Scholar] [CrossRef]
- Lu, T.; Chen, F.W. Multiwfn: A Multifunctional Wavefunction Analyzer. J. Comput. Chem. 2012, 33, 580–592. [Google Scholar] [CrossRef] [PubMed]
- Bader, R. Atoms in Molecules: A Quantum Theory; Oxford University Press: Oxford, UK, 1990. [Google Scholar]
- Nalewajski, R.F.; Mrozek, J. Modified valence indices from the two-particle density matrix. Int. J. Quantum Chem. 1994, 51, 187. [Google Scholar] [CrossRef]
- Nalewajski, R.F.; Mrozek, J.; Michalak, A. Two-electron valence indices from the Kohn-Sham orbitals. Int. J. Quantum Chem. 1997, 61, 589. [Google Scholar] [CrossRef]
- Hoffmann, R. Solids and Surfaces: A Chemist’s View of Bonding in Extended Structures; Wiley VCH: New York, NY, USA, 1988. [Google Scholar]
- Małecki, J.G. Synthesis, crystal, molecular and electronic structures of thiocyanate ruthenium complexes with pyridine and its derivatives as ligands. Polyhedron 2010, 29, 1973. [Google Scholar] [CrossRef]
- Lu, T.; Chen, F.W. Meaning and Functional Form of the Electron Localization Function. Acta Phys. Chim. Sin. 2011, 27, 2786–2792. [Google Scholar]
- Fonseca Guerra, C.; Handgraaf, J.W.; Baerends, E.J.; Bickelhaupt, F.M. Voronoi Deformation Density (VDD) Charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD Methods for Charge analysis. J. Comput. Chem. 2004, 25, 189. [Google Scholar] [CrossRef]
- Barone, V.; Cossi, M. Quantum calculation of molecular energies and energy gradients in solution by a conductor solvent model. J. Phys. Chem. A 1998, 102, 1995. [Google Scholar] [CrossRef]
B28 | B32 | B34 | B36 | B38 | B40 | |
---|---|---|---|---|---|---|
U | 2.57 | 2.55 | 2.54 | 2.49 | 2.52 | 2.57 |
(2.62) | (2.59) | (2.58) | (2.56) | (2.56) | (2.59) | |
Np | 2.59 | 2.55 | 2.55 | 2.52 | 2.52 | 2.57 |
(2.64) | (2.62) | (2.60) | (2.59) | (2.58) | (2.61) | |
Pu | 2.60 | 2.57 | 2.56 | 2.54 | 2.53 | 2.59 |
(2.64) | (2.63) | (2.61) | (2.62) | (2.59) | (2.65) |
Species | Bond | ρ(r) | G(r) | V(r) | H(r) | −V(r)/G(r) | ELF | |
---|---|---|---|---|---|---|---|---|
UB36 | U-B1 | 0.084 | 0.090 | 0.052 | −0.082 | −0.030 | 1.569 | 0.446 |
U-B6 | 0.084 | 0.092 | 0.053 | −0.082 | −0.029 | 1.560 | 0.440 | |
NpB36 | Np-B1 | 0.077 | 0.096 | 0.049 | −0.073 | −0.025 | 1.505 | 0.406 |
Np-B6 | 0.077 | 0.096 | 0.049 | −0.073 | −0.025 | 1.505 | 0.405 | |
PuB36 | Pu-B1 | 0.073 | 0.103 | 0.048 | −0.070 | −0.022 | 1.461 | 0.375 |
Pu-B6 | 0.073 | 0.103 | 0.048 | −0.070 | −0.022 | 1.461 | 0.375 |
Species | 2S + 1 | Bond | r(Å) | FBO | Hirshfeld |
---|---|---|---|---|---|
U&B36 | 3 | U-B1 | 2.36 | 1.04 | −4.28739 (U) |
U-B6 | 2.36 | 1.06 | |||
Np&B36 | 4 | Np-B1 | 2.39 | 0.97 | −4.34314 (Np) |
Np-B6 | 2.39 | 0.97 | |||
Pu&B36 | 5 | Pu-B1 | 2.40 | 0.97 | −4.35974 (Pu) |
Pu-B6 | 2.40 | 0.97 |
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Li, P.; Wei, J.; Wei, H.; Wang, K.; Wu, J.; Li, Y.; Liu, W.; Fu, Y.; **e, F.; Ma, J. A Systemic Insight into Exohedral Actinides and Endohedral Borospherenes: An&Bm and An@Bn (An=U, Np, Pu; m = 28, 32, 34, 36, 38, 40; n = 36, 38, 40). Molecules 2022, 27, 6047. https://doi.org/10.3390/molecules27186047
Li P, Wei J, Wei H, Wang K, Wu J, Li Y, Liu W, Fu Y, **e F, Ma J. A Systemic Insight into Exohedral Actinides and Endohedral Borospherenes: An&Bm and An@Bn (An=U, Np, Pu; m = 28, 32, 34, 36, 38, 40; n = 36, 38, 40). Molecules. 2022; 27(18):6047. https://doi.org/10.3390/molecules27186047
Chicago/Turabian StyleLi, Peng, **gbo Wei, Hao Wei, Kerong Wang, Jizhou Wu, Yuqing Li, Wenliang Liu, Yongming Fu, Feng **e, and Jie Ma. 2022. "A Systemic Insight into Exohedral Actinides and Endohedral Borospherenes: An&Bm and An@Bn (An=U, Np, Pu; m = 28, 32, 34, 36, 38, 40; n = 36, 38, 40)" Molecules 27, no. 18: 6047. https://doi.org/10.3390/molecules27186047