含非金属原子核的异核超卤素阴离子$\mathrm{MXO}_{4}^{-}$的理论计算

Theoretical Calculation of Heteronuclear Superhalogen Anions $\mathrm{MXO}_{4}^{-}$ Containing Nonmetallic Atomic Nuclei

摘要

基于超卤素的高电子亲和能(EA)独特的化学性质和广泛的应用前景,以碱土金属(Be,Mg,Ca)和氮族非金属(N,P)为中心原子,以O原子为配体,构建异双核超卤素阴离子$\mathrm{MXO}_{4}^{-}$ (M=Be,Mg,Ca;X=N,P),并通过理论计算研究其几何结构、相对稳定性及垂直电子脱附能(VDE).结果表明: $\mathrm{MXO}_{4}^{-}$可分为含0个、1个、2个或3个桥连O原子(0,1,2,3)4类几何构型,其中结构2的VDE值最高,结构0的VDE值最低;中心原子的半径和种类对VDE值影响显著,金属中心原子M半径越小,非金属中心原子X的电负性越大,阴离子的VDE值越高.

Abstract

Based on the unique chemical properties and broad application prospects of high electron affinity (EA) of superhalogens, we constructed a hetero-binuclear superhalogen anions $\mathrm{MXO}_{4}^{-}$ (M=Be, Mg, Ca; X=N, P) with alkaline earth metals (Be, Mg, Ca) and pnictogen nonmetals (N, P) as central atoms, and oxygen atoms as ligands, and studied its geometric structures, relative stabilities, and vertical detachment energies (VDE) through theoretical calculations. The results show that the $\mathrm{MXO}_{4}^{-}$ can be classified into four geometric configurations containing zero, one, two or three bridged oxygen atoms (0, 1, 2, 3), with structure 2 having the highest VDE values, and structure 0 having the lowest VDE values. The radius and type of central atoms significantly influence the VDE values, the smaller radii of the metal central atom M, the greater the electronegativity of the nonmetal central atom X, and the higher the VDE value of the anions.

关键词

超卤素阴离子 / 异双核 / 非金属核 / 垂直电子脱附能 / 理论计算

Key words

superhalogen anion / hetero-binuclear / nonmetal nuclear / vertical detachment energy / theoretical calculation

参考文献

[1] Gustev G, Boldyrev A. DVM-Xα Calculations on the Ionization Potentials of MX^-_k+1 Complex Anions and the Electron Affinities of MX_k+1 “Superhalogens”[J]. Chemical Physics, 1981, 56(3): 277-283.

[2] Bartlen N. Xenon Hexafluoroplatinate(Ⅴ) Xe⁺[PtF₆]^-[J]. Chemical Society, 1962: 218.

[3] Srivastava A K. Ionization of NO by Superhalogens: DFT and QTAIM Approaches[J]. Main Group Chemistry, 2021, 20(1): 33-40.

[4] Bartlett N, Lohmann D. Fluorides of the Noble Metals. Part Ⅱ. Dioxygenyl Hexafluoroplatinate (Ⅴ), $\mathrm{O}_{2}^{+}\left[\mathrm{PtF}_{6}\right]^{-}$[J]. Journal of the Chemical Society, 1962: 5253-5261.

[5] Celina S. Oxidizing Metal Oxides with Polynuclear Superhalogen: An ab Initio Study[J]. The Journal of Physical Chemistry A, 2018, 122(37): 7328-7338.

[6] Chang X T, Li Y, Liu J Y, et al. Noble Gas Insertion Compounds of Hydrogenated and Lithiated Hyperhalogens[J]. Physical Chemistry Chemical Physics, 2019, 21(36): 20156-20165.

[7] Kosar N, Ashraf T, Imran M, et al. Amplifying the Nonlinear Optical Response of Sunflower-Like C₁₆S₈ through Superhalogen Doping[J]. Physica Scripta, 2024, 99(6): 065206-1-065206-15.

[8] Yang H, Li Y, Wu D, et al. Structural Properties and Nonlinear Optical Responses of Superatom Compounds BF₄-M (M=Li, FLi₂, OLi₃, NLi₄)[J]. International Journal of Quantum Chemistry, 2012, 112(3): 770-778.

[9] Xiong M, Kong C C, Yang Z M, et al. Superhalogens Inside Fullerenes X@C_2n (X=BO₂, BeF₃; 2n=60, 70)[J]. Physical Chemistry Chemical Physics, 2024, 26(31): 21282-21289.

[10] Zhang H, Xu S D, Guo T L, et al. Dual Effect of Superhalogen Ionic Liquids Ensures Efficient Carrier Transport for Highly Efficient and Stable Perovskite Solar Cells[J]. ACS Applied Materials & Interfaces, 2022, 14(25): 28826-28833.

[11] Lu S J, Cao G J, Gao Z O, et al. Structural and Electronic Insights into $\mathrm{Au}_{2} \mathrm{C}_{20}^{-}$ Cluster: A Superhalogen with Dual Aromaticity[J]. Chemical Physics Letters, 2025, 860: 141814-1-141814-7.

[12] Morgan H, Tan H B T, Derevianko A, et al. Design of New Thorium Nuclear Clock Materials Based on Polyatomic Ions[J]. Dalton Transactions, 2025, 54: 10574-1-10574-7.

[13] Srivastava A K. $\left[\mathrm{NH}_{4}^{+}\right]\left[\mathrm{B}_{x} \mathrm{H}_{3 x+1}^{-}\right](x=1-5)$: Role of Polynuclear Superhalogens in High-Capacity Hydrogen Storage[J]. Inorganic Chemistry, 2024, 63(29): 13425-13430.

[14] Srivastava A K, Kumar A, Tiwari S N, et al. Application of Superhalogens in the Design of Organic Superconductors[J]. New Journal of Chemistry, 2017, 41(24): 14847-14850.

[15] Fang H, Wang S, Liu J Y, et al. Superhalogen-Based Lithium Superionic Conductors[J]. Journal of Materials Chemistry A, 2017, 5(26): 13373-13381.

[16] Tripathi J K, Srivastava A K. Superhalogens and Superalkalis[M]. Boca Raton: CRC Press, 2024: 246-260.

[17] Giri S, Behera S, Jena P. Superalkalis and Superhalogens as Building Blocks of Supersalts[J]. The Journal of Physical Chemistry A, 2014, 118(3): 638-645.

[18] Srivastava A K. Prediction of Novel Liquid Crystalline Molecule Based on BO₂ Superhalogen[J]. Journal of Molecular Liquids, 2021, 344: 117968-1-117968-5.

[19] Parida R, Reddy G N, Chakraborty A, et al. A New Class of Superhalogen Based Anion Receptor in Li-Ion Battery Electrolytes[J]. Journal of Chemical Information and Modeling, 2019, 59(5): 2159-2164.

[20] Wang X B, Ding C F, Wang L S, et al. First Experimental Photoelectron Spectra of Superhalogens and Their Theoretical Interpretations[J]. The Journal of Chemical Physics, 1999, 110(10): 4763-4771.

[21] Elliott B M, Koyle E, Boldrev A I, et al. $\mathrm{MX}_{3}^{-}$ Superhalogens (M=Be, Mg, Ca; X=Cl, Br): A Photoelectron Spectroscopic and ab Initio Theoretical Study[J]. The Journal of Physical Chemistry A, 2005, 109(50): 11560-11567.

[22] Yang X, Wang X B, Wang L S, et al. On the Electronic Structures of Gaseous Transition Metal Halide Complexes, $\mathrm{FeX}_{4}^{-}$ and $\mathrm{MX}_{3}^{-}$ (M=Mn, Fe, Co, Ni, X=Cl, Br), Using Photoelectron Spectroscopy and Density Functional Calculations[J]. The Journal of Chemical Physics, 2003, 119(16): 8311-8320.

[23] Anusiewicz I, Skurski P. Unusual Structures of $\mathrm{Mg}_{2} \mathrm{-F}_{5}^{-}$ Superhalogen Anion[J]. Chemical Physics Letters, 2007, 440(1/2/3): 41-44.

[24] Zhai H J, Wang L M, Li S D, et al. Vibrationally Resolved Photoelectron Spectroscopy of BO^- and $\mathrm{BO}_{2}^{-}$: A Joint Experimental and Theoretical Study[J]. The Journal of Physical Chemistry A, 2007, 111(6): 1030-1035.

[25] Anusiweicz I. Superhalogen Anions Utilizing Acidic Functional Groups as Ligands[J]. The Journal of Physical Chemistry A, 2009, 113(42): 11429-11434.

[26] Anusiewicz I. Electrophilic Substituents as Ligands in Superhalogen Anions[J]. The Journal of Physical Chemistry A, 2009, 113(23): 6511-6516.

[27] Freza S, Skurski P. Enormously Large (Approaching 14 eV!) Electron Binding Energies of [H_nF_n+1]^- (n=1-5, 7, 9, 12) Anions[J]. Chemical Physics Letters, 2010, 487(1/2/3): 19-23.

[28] Pathak B, Samanta D, Ahuja R, et al. Borane Derivatives: A New Class of Super- and Hyperhalogens[J]. ChemPhysChem, 2011, 12(13): 2423-2428.

[29] Sun W M, Li X H, Li Y, et al. Can Fluorinated Molecular Cages Be Utilized as Building Blocks of Hyperhalogens?[J]. ChemPhysChem, 2016, 17(10): 1468-1474.

[30] Yang H, Li Y, Zhao J G, et al. On Structure and Hyperhalogen Properties of Hetero-Binuclear Superatoms $\mathrm{MM}^{\prime}\left(\mathrm{BO}_{2}\right)_{n}^{-}\left(\mathrm{M}=\mathrm{Na}, \mathrm{Mg} ; \mathrm{M}^{\prime}=\mathrm{Mg}, \mathrm{Al} ; n=4-6\right) $[J]. Polyhedron, 2021, 209: 115456-1-115456-6.

[31] Xue Q Q, Zhong M M, Zhou J, et al. Rational Design of Endohedral Superhalogens without Using Metal Cations and Electron Counting Rules[J]. The Journal of Physical Chemistry A, 2022, 126(22): 3536-3542.

[32] Freza S, Cyraniak A, Wiszowska N, et al. Excess Electron Binding Energy Approaching 15 eV in Polynuclear Antimony Fluoride Anions: From Small Structures to Nanoparticle-Sized Systems[J]. Chemical Physics Letters, 2025, 861: 141828-1-141828-8.

[33] Yan H F, Guo J C. HLi₄Cl^-₄: A Planar Tetracoordinate Hydrogen Superhalogen Anion[J]. Physical Chemistry Chemical Physics, 2025, 27(14): 7383-7388.

[34] Yang H, Li Y, He H M, et al. Superhalogen Properties of Hetero-Binuclear Anions $\mathrm{MM}^{\prime} \mathrm{F}_{4}^{-}$ and $\mathrm{MM}^{\prime \prime} \mathrm{F}_{5}^{-}$ (M=Li, Na, M′=Be, Mg, Ca; M″=B, Al, Ga)[J]. Chemical Physics Letters, 2017, 684: 273-278.

[35] Yang H, Li Y, He H M, et al. Hetero-Binuclear Superhalogen Anions with Cyanide and/or Isocyanide as Ligands[J]. Chemical Physics Letters, 2018, 713: 203-209.

[36] Yang H, He H M, Li N, et al. Design of a Novel Series of Hetero-Binuclear Superhalogen Anions $\mathrm{MM}^{\prime} \mathrm{X}_{4}^{-}$ (M=Li, Na; M′=Be, Mg, Ca; X=Cl, Br)[J]. Frontiers in Chemistry, 2022, 10: 936936-1-936936-7.

[37] Møller C, Plesset M S. Note on an Approximation Treatment for Many-Electron Systems[J]. Physical Review, 1934, 46(7): 618-622.

[38] Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian 16[CP/CD]. Wallingford CT: Gaussian Inc., 2016.

[39] Dennington R, Keith T, Millan J, et al. GaussView (Version 6.0)[CP/CD]. Shawnee Mission KS: Semichem Inc., 2016.

基金资助

国家自然科学基金(52071192)

山西省基础研究计划青年科学研究项目(202203021222296)

山西省高等学校科技创新项目(2023L254)

山西大同大学博士科研项目(2019-B-11)

山西大同大学大学生创新实验项目(2023-83)