超原子
外觀
超原子是一個表現出元素的原子性質的原子團簇。鈉原子從蒸汽冷卻時自然凝結成團簇時優先含有原子個數為(2,8,20,40,58等)的幻數。前兩個可以被看作是需要分別填充的第一和第二殼的電子數目。超原子中的自由電子占據整個的原子團外層,而不是分散在單個的原子上。價電子光譜性質及團簇作為整體所具有的化學價態要與相應的原子相似。根據超原子特殊的物理化學特性及潛在的應用價值,有人提出了三維元素周期表的概念[1]。比如TiO、ZrO和WC分別是金屬Ni、Pd和Pt的「超級原子」。
鋁原子簇
[編輯]磁性超原子
[編輯]在過渡金屬中摻雜的金屬超原子中同時存在近自由電子軌道和局域d軌道,d軌道電子貢獻了超原子磁矩,而其他近自由電子使超原子具有高穩定性[6]。
- CsNa8 = 性質類似於單個Mn原子
- TiNan(n=1~13)
- FeMg8 = 兼具磁性和導電性
- VCs8 = 兼具磁性和導電性
- ScCs12
- MnAuz4(SH)18
超鹵素
[編輯]化合物具有超鹵素(superhalogen)特性用MXk+1−來表示,M代表一個主族(包含氫原子 )或過渡金屬原子,X代表一個鹵素原子,k代表M原子的最正價。
- MX2−(M=Li,Na;X=Cl,Br,I)
- MgX3−、CaX3−(X=F,Cl,Br).
- Mg2F5−
- Mg2Cl5−、Mg2Cl7−
- BX4−、AlX4−(X=F,Cl,Br)
- Al(BH4)n=l~4、Al(BF4)n=l~4
- MC14−(M=Sc,Y,La)
超鹼金屬
[編輯]化合物具有超鹼金屬特性用YMk+1來表示,Y代表一個主族或過渡金屬原子,M代表一個鹼金屬原子,k代表Y原子的最高負價。
- XLin(n=2,3;X=F,CI,Br,I)
- OM3(M=Li,Na,K)
- LinFn+(n=3,4)
- NLil5
- BLil5
- Na2X(X=SH,SCH3,OCH3,CN,N3)
- Na2XY(X=同上)(Y=MgCl3,Cl,NO2).
- B2Li11
- M2Li2k+1+ (k=3,5,7;M=F,O,N,C,respeetively)
超鹵素超鹼金屬化合物
[編輯]由於超鹵素,超鹼金屬團簇特殊的氧化還原特性 ,因此具有合成超原子間形成的分子(supermolecule)這一類新複合物的可能。
- (Li3)+(SH)-(SH=LiF2,BeF3, BF,4)
- LiBeX3(X=F,Cl,Br)
- BLi6X(X=F,LiF2,BeF3,BF4)
其它超原子
[編輯]- Ag9
- Ag13
- Ag55
- C60 = 富勒烯及其衍生物的也具有超原子態[7]
- 當碳納米管/氮化硼納米管軸對稱的近自由電子鍵投影到垂直於軸的平面時,也可以觀察到與原子軌道相似的超原子態[8]
- Li(HF)3Li = (HF)3 就像原子核[9]
- VSi16F = 具有離子鍵[10]
- 13個鉑原子的原子簇[11]
- 2000個銣原子的原子簇[12]
配體金屬團簇超原子
[編輯]核心是金屬超原子的有機配體金屬團簇。
金配體金屬團簇超原子
[編輯]- RS(AuSR)2 [13]
- Aun(SR)n−1
- Aun(SR)n+1
- Aum(S)n -
- Aum(SR)n+
- Au25–nAgn(SH)1818- (n = 1, 2, 4, 6, 8, 10, 12) [14]
- Au25(SMe)18− [15]
- Au25(SR)18−
- XAu24(SR)18 (X=Mn,Pd, Ag,Cd)
- Au24(SR)20
- Au102(p-MBA)44 [16][17]
- Au102(SR)44
- Au144(SR)60 [18]
其它配體金屬團簇超原子
[編輯]參看
[編輯]參考
[編輯]- ^ Denis E.Berger0n,A.Welford Castleman Jr.,Tsuguo Morisato and Shiv N.Khanna.Formation of Al13I-: Evidence for the Superhalogen Character of Al13,Science. 2004,84:304.
- ^ Formation of Al13I−: Evidence for the Superhalogen Character of Al13 D. E. Bergeron, A.W. Castleman Jr., T. Morisato, S. N. Khanna Science, Vol 304, Issue 5667, 84–87 , 2 April 2004 Abstract (頁面存檔備份,存於網際網路檔案館) MS spectra (頁面存檔備份,存於網際網路檔案館)
- ^ 3.0 3.1 Naiche Owen Jones, 2006.[失效連結]
- ^ Philip Ball, "A New Kind of Alchemy", New Scientist Issue dated 2005-04-16.
- ^ Al Cluster Superatoms as Halogens in Polyhalides and as Alkaline Earths in Iodide Salts D. E. Bergeron, P. J. Roach, A.W. Castleman Jr., N.O. Jones, S. N. Khanna Science, Vol 307, Issue 5707, 231–235 , 14 January 2005 Abstract (頁面存檔備份,存於網際網路檔案館) MS spectrum (頁面存檔備份,存於網際網路檔案館)
- ^ Reveles J.U,Clayborne P.A,Reber A.C,Khanna S.N, Pradhan K,Sen P and Pederson M.R.Designer magnetic superatoms.Na—ture Chem. 2009,1:310.
- ^ Min Feng,Jin Zhao,Hrvoje Petek.Science,2008,320:359.
- ^ Pablo D.Jadzinsky,Guillermo Calero,Christopher J.Ackerson,David A.Bushnell and Roger D.Kornberg.Structure of a Thiol Mono-layer-Protected Gold Nanoparticle at 1.1A Resolution.Science. 2007,318:430.
- ^ Extraordinary superatom containing double shell nucleus: Li(HF)3Li connected mainly by intermolecular interactions, Sun, Xiao-Ying, Li, Zhi-Ru, Wu, Di, & Sun, Chia-Chung, 2007.
- ^ Electronic and geometric stabilities of clusters with transition metal encapsulated by silicon 網際網路檔案館的存檔,存檔日期2011-05-22., Kiichirou Koyasu et al.
- ^ Platinum nanoclusters go magnetic (頁面存檔備份,存於網際網路檔案館), nanotechweb.org, 2007
- ^ Ultra Cold Trap Yields Superatom 網際網路檔案館的存檔,存檔日期2008-07-06., NIST, 1995
- ^ De—anJiang,RobertL.Whetten,WeidongLuoandShengDai.The Smallest Thiolated Gold Superatom Complexes.J.Pbys.Chem.c.2009,l13,l7291.
- ^ Emilie B. Guidez, Ville Mäkinen , Hannu Häkkinen, and Christine M. Aikens,Effects of Silver Doping on the Geometric and Electronic Structure and Optical Absorption Spectra of the Au25–nAgn(SH)1818- (n = 1, 2, 4, 6, 8, 10, 12) Bimetallic Nanoclusters,J. Phys. Chem. C, 2012, 116 (38), pp 20617–20624,DOI: 10.1021/jp306885u
- ^ J. Akola, M. Walter, R.L. Whetten, H. Häkkinen and H. Grönbeck, "On the structure of thiolate-protected Au25", JACS (頁面存檔備份,存於網際網路檔案館) 130, 3756–3757 (2008)
- ^ M. Walter, J. Akola, O. Lopez-Acevedo, P. D. Jadzinsky, G. Calero, C. J. Ackerson, R. L. Whetten, H. Grönbeck, H. Häkkinen, Gold Superatom Complexes (頁面存檔備份,存於網際網路檔案館)"A unified view of ligand-protected gold clusters as superatom complexes ", PNAS 105, 9157 (2008)
- ^ P.D. Jadzinsky, G. Calero, C.J. Ackerson, D.A. Bushnell, R.D. Kornberg, Gold Superatom Complexes (頁面存檔備份,存於網際網路檔案館) Structure of a thiol monolayer-protected gold nanoparticle at 1.1 Å resolution" Science 318, 430–433 (2007)
- ^ O. Lopez-Acevedo, J. Akola, R.L. Whetten, H. Grönbeck, H. Häkkinen, "Structure and Bonding in the Ubiquitous Icosahedral Metallic Gold Cluster Au144(SR)60", JPCC (頁面存檔備份,存於網際網路檔案館) 130, 3756–3757 (2009)
- ^ J. Hartig, A. Stösser, H. Schnöckel, "A metalloid (Ga23{N(SiMe3)2}11) cluster: The jellium model put to test" Angew. Chemie. Int. Ed. 46, 1658–1662 (2007).
- ^ P.A. Clayborne, O. Lopez-Acevedo, R.L. Whetten, H. Grönbeck and H. Häkkinen, 「Al50Cp*12 Cluster: A 138-electron (L=6) Superatom」, Eur. J. Inorg. Chem. (頁面存檔備份,存於網際網路檔案館) 2011.
外部連結
[編輯]- Designer Magnetic Superatoms (頁面存檔備份,存於網際網路檔案館), J.U. Reveles, et al. 2009
- Gold Superatom Complexes (頁面存檔備份,存於網際網路檔案館), M. Walter et al. 2008
- Gold Superatom Complexes (頁面存檔備份,存於網際網路檔案館) P.D. Jadzinsky et al. 2007
- Multiple Valence Superatoms (頁面存檔備份,存於網際網路檔案館), J.U. Reveles, S.N. Khanna, P.J. Roach, and A.W. Castleman Jr., 2006
- On the Aluminum Cluster Superatoms acting as Halogens and Alkaline-earth Metals, Bergeron, Dennis E et al., 2006
- Beyond The Periodic Table[永久失效連結], Computational Chemistry Portal, 2006
- Expanding the periodic table? The Scientist, 2005
- Clusters of Aluminum Atoms Found to Have Properties of Other Elements Reveal a New Form of Chemistry (頁面存檔備份,存於網際網路檔案館), innovations report, 2005. Have a picture of Al14.
- Clusters of Aluminum Atoms Found to Have Properties of Other Elements Reveal a New Form of Chemistry, Penn State, Eberly College of Science, 2005
- Research Reveals Halogen Characteristics innovations report, 2004. Have pictures of Al13.