NO在金属Be_n(n=2-12)团簇表面的平行吸附
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摘要
采用密度泛函理论(DFT)中的广义梯度近似(GGA),对Be_nNO (n=2-12)团簇进行了构型优化,稳定性和电子性质分析.结果表明:从n=3开始,Be_nNO的基态均为NO分子平行吸附于主团簇Be_n某一表面时形成的,此时N-O键自然断裂(N-O键伸长量均超过了100%),而N端吸附于Be-Be桥位的结构仅是Be_nNO (n=2-12)团簇的一个亚稳态结构.成键性质分析表明,NO平行吸附时,N,O原子倾向于同时吸附于近邻的三个Be原子面位,相应的Be_n团簇表现出了很好的吸附能力.此时N, O原子的sp~3轨道杂化出现的孤对电子对N-O键的断裂产生了重要影响.
The geometry structures, stabilities and chemical bonding properties of the Be_nNO(n=2-12) clusters have been studied within the framework of the generalized gradient approximation(GGA) based on the density functional theory(DFT). The results show that the ground state structures of Be_nNO(n=2-12) are obtained as NO is parallel adsorbed on one surface of corresponding host Be_n cluster, coupled with the natural break of N-O bonds(the elongation N-O distance is more than 100% in all of the cases). The structure, with N atom being adsorbed on the Be-Be bridge site, is only a metastability. The analysis of bonding properties suggests that the appearance of the unpaired electron, arising from the sp~3 hybridization of N and O atom, note only leads to the fracture of N-O bond, but also gives rise to the improvement of the N-Be and O-Be bond, which has an important effects on the exhibition of good ability for Be_n clusters to adsorb NO molecules.
The geometry structures, stabilities and chemical bonding properties of the Be_nNO(n=2-12) clusters have been studied within the framework of the generalized gradient approximation(GGA) based on the density functional theory(DFT). The results show that the ground state structures of Be_nNO(n=2-12) are obtained as NO is parallel adsorbed on one surface of corresponding host Be_n cluster, coupled with the natural break of N-O bonds(the elongation N-O distance is more than 100% in all of the cases). The structure, with N atom being adsorbed on the Be-Be bridge site, is only a metastability. The analysis of bonding properties suggests that the appearance of the unpaired electron, arising from the sp~3 hybridization of N and O atom, note only leads to the fracture of N-O bond, but also gives rise to the improvement of the N-Be and O-Be bond, which has an important effects on the exhibition of good ability for Be_n clusters to adsorb NO molecules.
引文
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[3] Wang Y W,Lin C D,Liang J,et al.Neural correlates of audio-visual modal interference inhibition investigated in children by ERP [J].Sci.China Chem.,2011,54:194.
[4] He C Z,Wang H,Huai L Y,et al.First-principles study on NO adsorption and dissociation on O-Predosed Ir (100) [J].Chem.J.Chinese Univ.,2013,34:946 (in Chinese) [何朝政,王会,淮丽媛,等.NO在氧预吸附Ir(100)表面吸附和解离的第一性原理研究 [J].高等学校化学学报,2013,34:946]
[5] Fu L,Zhang S,Lv L X,et al.NO adsorption and decomposition on Ir(111) surface:A first principles study[J].J.At.Mol.Phys.,2018,35:395 (in Chinese) [付玲,张帅,吕林霞,等.NO在Ir(111)表面吸附与解离的第一性原理研究[J].原子与分子物理学报,2018,35:395]
[6] Sun L H,Hu J,Gao F,et al.First-principle study of NO adsorption on the LaFeO3 (010) surface [J].Phys.B,2011,406:4105.
[7] Ghosh P,Pushpa R,Gironcoli S.de,et al.Interplay between bonding and magnetism in the adsorption of NO on Rh clusters [J].J.Chem.Phys.,2008,128:389.
[8] Danilczuk M,Lund A.Adsorption of NO in Li-exchanged zeolite A.A density functional theory study [J].Chem.Phys.Lett.,2010,490:205.
[9] Lv B,LingHu R F,Song X S,et al.The vibration and dissociation of NO on Pt (111) surface [J].Acta Phys.Sin.,2012,61:226801 (in Chinese) [吕兵,令狐荣锋,宋晓书,等.NO在Pt(111)表面的振动和离解 [J].物理学报,2012,61:226801]
[10] Xu X L,Chen W K,Wang X,et al.A DFT study on the adsorption of NO on CuCr2O4 (100) surface [J].Chin.J.Inorg.Chem.,2007,23:1375 (in Chinese) [徐香兰,陈文凯,王霞,等.密度泛函理论研究NO在CuCr2O4 (100) 表面的吸附 [J].无机化学学报,2007,23:1375]
[11] Yao J G,Gong B A,Wang Y X.Dissociative adsorptions of NO on Yn (n=1-12) clusters [J].Acta Phys.Sin.,2013,62:243601 (in Chinese) [姚建刚,宫宝安,王渊旭,NO在Yn(n=1-12)团簇表面的解离性吸附 [J].物理学报,2013,62:243601]
[12] Doerner R P.The implications of mixed-material plasma-facing surfaces in ITER [J].J.Nucl.Mater.,2007,363:32.
[13] Reinelt M,Linsmeier C.Temperature programmed desorption of 1 keV deuterium implanted into clean beryllium [J].Phys.Scr.,2007,T128:111.
[14] Marino M M,Ermler W C,Tompa G S,et al.Effects of hydrogen and of cesium adsorption on a beryllium surface:A theoretical and experimental study [J].Surf.Sci.,1989,208:189.
[15] Ray K B,Hannon J B,Plummer E W.An experimental study of hydrogen adsorption on beryllium [J].Chem.Phys.Lett.,1990,171:469.
[16] Ning H,Tao X M,Wang M M,et al.Density Functional Theory Study on Hydrogen Adsorption on Be(0001) Surface[J].Acta Phys.-Chim.Sin.,2010,26:2267 (in Chinese) [宁华,陶向明,王芒芒,等.氢原子在Be(0001)表面吸附的密度泛函理论研究[J].物理化学学报,2010,26:2267]
[17] Ning H,Tao X M,Tan M Q.Water adsorption on the Be (0001) surface:from monomer to trimer adsorption [J].Chin.Phys.B,2012,21:016802.
[18] Lee C,Yang W,Parr R G.Density-functional exchange-energy approximation with correct asymptotic behavior [J].Phys.Rev.A,1988,38:3098.
[19] Becke A D.A multicenter numerical integration scheme for polyatomic molecules [J].J.Chem.Phys.,1988,88:2547.
[20] Delley B.From molecules to solids with the DMol 3 approach [J].J.Chem.Phys.,2000,113:7756.
[21] Huber K P,Herzberg G.Molecular spectra and molecular structure.IV.Constants of diatomic molecules [M].New York:Van Norstrand,1979.
[22] Bondybey V E.Electronic structure and bonding of Be2 [J].Phys.Lett.,1984,109:436.
[23] Lide D R.CRC handbook of chemistry and physics [M].85th Edition.Boca Raton:CRC Press,2004.
[24] Herzberg G.Molecular structure I I.Infrared and Raman spectra of polyatomic molecules [M].New York:Van Norstrand,1945.
[25] Lei X L,Zhu H J,Wang X.M,et al.Equilibrium geometries and electronic properties of BenLi (n=2-15) clusters from first principles [J].Chin.Phys.B,2008,17:3687
[26] Lin M H,Xie Z X.Structural chemistry [M].Beijing:Science Press,2008:119 (in Chinese) [林梦海,谢兆雄.结构化学 [M].北京:科学出版社,2008:119]