[1]崔文文,王 成,王小亮,等.平面BnBe(n=1～7)团簇的结构和稳定性理论研究[J].南京师大学报(自然科学版),2013,36(03):61-65.
　Cui Wenwen,Wang Cheng,Wang Xiaoliang,et al.A Theoretical Study on Structure and Stability of Planar BnBe(n=1～7)[J].Journal of Nanjing Normal University(Natural Science Edition),2013,36(03):61-65.
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平面BnBe(n=1～7)团簇的结构和稳定性理论研究()
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《南京师大学报（自然科学版）》[ISSN:1001-4616/CN:32-1239/N]

卷:
第36卷
期数:
2013年03期
页码:
61-65
栏目:
化学
出版日期:
2013-09-30

文章信息/Info

Title:
A Theoretical Study on Structure and Stability of Planar BnBe(n=1～7)
作者:
崔文文; 王 成; 王小亮; 朱小蕾
南京工业大学化学化工学院,材料化学工程国家重点实验室,江苏 南京 210009
Author(s):
Cui Wenwen; Wang Cheng; Wang Xiaoliang; Zhu Xiaolei
State Key Laboratory of Materials-Oriented Chemical Engineering,College of Chemistry and Chemical Engineering, Nanjing University of Technology,Nanjing 210009,China
关键词:
硼铍团簇; 几何结构; 稳定性; 密度泛函
Keywords:
Beryllium boride cluster; geometry; stability; DFT
分类号:
O613.71
摘要:
运用密度泛函理论(DFT)对平面BnBe(n=1～7)的结构、稳定性及势能面进行了计算.通过计算得到了BnBe(n=1～7)团簇的最稳定结构.值得注意的是,BnBe(n=1～7)团簇的结构模式转变发生在n=1到n=2之间.平均原子成键能(BE)、成键能增量(IBE)、能量二次差分(Δ2E)和能隙(ΔE)的变化图揭示了B4Be和B7Be具有较高的稳定性.结果表明,BnBe(n=1～7)团簇的稳定性与离域π分子轨道、σ正切分子轨道和σ径向分子轨道的相互作用有关.价分子轨道和核独立化学位移(NICS)的分析证明异构体BnBe(n=2～5)都具有π-芳香性.理论分析表明,B4Be具有σ-和π-双芳香性.有趣的是,在CCSD(T)/6-311+G(d)//B3LYP/6-311+G(d)水平上,B4Be是热力学上和动力学上稳定的,可能在将来的实验中观察到.
Abstract:
The structures,stabilities,bonding nature,and potential energy surfaces of BnBe(n=1～7)are systematically explored and investigated based on density functional theory(DFT).The lowest-energy structures for BnBe(n=1～7)are located.It is worthy to note that a structural transition occurs from n=1 to n=2 for BnBe(n=1～7).The evolution of the binding energy per atom,incremental binding energy,second order difference of total energy,and energy gap with the size of BnBe reveals that the lowest-energy isomers B4Be and B7Be are highly stable.The results demonstrate that the stability of lowest-energy isomers of BnBe(n=1～7)is attributed to the delocalized π,σ-radial,and σ-tangential molecular orbitals(MOs)interactions.BnBe(n=2～5)exhibit π aromaticity from valence molecular orbital analysis and nucleus independent chemical shifts(NICSs)values.B4Be exhibit σ- and π-double aromaticity in terms of theoretical analyses.Interestingly,B4Be is stable both thermodynamically and kinetically,which may be observable in future experiment.

参考文献/References:

[1] Raghavachari K,Rohlfing C M.Structures of Si10.Are there conventionally bonded low-energy isomers?[J].Chem Phys Lett,1992,198(5):521-525.
[2]Zhu X L,Zeng X C.Structures and stabilities of small silicon clusters:ab initio molecular-orbital calculations of Si7-Si11[J].J Chem Phys,2003,118(8):3 558-3 570.
[3]Sands D E,Cline CF,Zalkin A,et al.The beryllium-boron system[J].Acta Cryst,1961,14(3):309-310.
[4]Imanishi N,Furuya T,Fujiwara I,et al.Chemical-bond dependence of Coulomb capture of pions in beryllium borides[J].Physical Review A,1985,32(5):2 584-2 588.
[5]Boldyrev A I,Gonzales N,Simons J.Periodicity and peculiarity in 120 first- and second-row diatomic molecules[J].J Chem Phys,1994,98(6):9 931-9 942.
[6]Güner O F,Lammertsma K.Structural and electronic properties of the tetraatomic B2Be2 cluster[J].J Am Chem Soc,1990,112(2):508-516.
[7]Niu J,Rao B K,Jena P.Atomic and electronic structures of neutral and charged boron and boron-rich clusters[J].J Chem Phys,1997,107(1):132-140.
[8]Li Q S,Jin Q.Theoretical study on the aromaticity of the pyramidal MB6(M=Be,Mg,Ca,and Sr)clusters[J].J Phys Chem A,2003,107(39):7 869-7 873.
[9]Li Q S,Jin Q.Aromaticity of planar B-5 anion in the MB5(M=Li,Na,K,Rb,and Cs)and MB+5(M=Be,Mg,Ca,and Sr)clusters[J].J Phys Chem A,2004,108(5):855-860.
[10]Feng P Z,Fa G M,Shu L Q.MB2-8,(M=Be,Mg,Ca,Sr,and Ba):planar octacoordinate alkaline earth metal atoms enclosed by boron rings[J].Sci China Chem,2010,53(8):1 737-1 745.
[11]Benhelal O,Laksari S,Chahed A,et al.Full-potential study of structural and electronic properties of MB2-type metal diborides(M=Be,Mg and Ca)[J].Computational Materials Science,2011,50(6):1 889-1 893.
[12]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian 09,Revision A.02[M].Wallingford:Gaussian Inc,2009.
[13]Lee C,Yang W,Parr R G.Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density[J].Phys Rev B,1988,37(2):785-789.
[14]Pople J A,Head-Gordon M,Raghavachari K.Quadratic configuration interaction:a general technique for determining electron correlation energies[J].J Chem Phys,1987,87(10):5 968-5 975.
[15]Drummond M L,Meunier V,Sumpter B G.Structure and stability of small boron and boron oxide clusters[J].J Phys Chem A,2007,111(28):6 539-6 551.
[16]Raghavachari K,Binkley J S.Structure,stability,and fragmentation of small carbon clusters[J].J Chem Phys,1987,87(4):2 191-2 197.
[17]Schleyer P v R,Jiao H J,Hommes N J R v E,et al.An evaluation of the aromaticity of inorganic rings:refined evidence from magnetic properties[J].J Am Chem Soc,1997,119(1):12 669-12 670.
[18]Lu T,Chen F W.Multiwfn:a multifunctional wavefunction analyzer[J].J Comput Chem,2012,33(5):580-592.

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备注/Memo

备注/Memo:
收稿日期:2013-01-08.
基金项目:国家自然科学基金(21276122、21136001、20876073).
通讯联系人:朱小蕾,教授,博士生导师,研究方向:分子模拟.E-mail:xlzhu@njut.edu.cn
更新日期/Last Update: 2013-09-30