物理化学学报
物理化學學報
물이화학학보
ACTA PHYSICO-CHIMICA SINICA
2014年
12期
2233-2240
,共8页
硼金团簇%铝金团簇%适应性自然密度划分%电子局域函数%光电子能谱
硼金糰簇%鋁金糰簇%適應性自然密度劃分%電子跼域函數%光電子能譜
붕금단족%려금단족%괄응성자연밀도화분%전자국역함수%광전자능보
Boron auride%Aluminum auride%Adaptive natural density partitioning%Electron localization function%Photoelectron spectroscopy
Au/H相似性的研究是现代化学中的一个热门话题.我们从理论上报道Au/H相似的新成员：共价化合物B2Au4,离子化合物Al2Au4和BAlAu4.采用密度泛函和波函数理论方法对比研究了缺电子体系B2Au4、Al2Au4和BAlAu4的几何和电子结构.详细讨论了它们基态结构的轨道、适应性自然密度划分(AdNDP)和电子局域函数(ELF)分析.计算结果表明稍微扭曲变形的C2 B2Au4是基态结构,在这个共价化合物中含有两个B―Au―B三中心二电子(3c-2e)键.然而C3v Al+(AlAu4)-和C3v Al+(BAu4)-被研究证明是含有三个X―Au―Al三中心二电子键的类盐化合物(在Al2Au4中X=Al, BAlAu4中X=B). Al2Au4和BAlAu4是至今为止首例报道的在离子缺电子体系中含有金桥键的化合物.同时计算了B2Au4-、Al2Au4-和BAlAu4-阴离子基态结构的绝热剥离能和垂直剥离能,为实验表征提供依据.文中报道的金桥键为共价键和离子键相结合的缺电子体系提供了一个有趣的键合模式,有助于设计含有高度分散金原子的新材料和催化剂.
Au/H相似性的研究是現代化學中的一箇熱門話題.我們從理論上報道Au/H相似的新成員：共價化閤物B2Au4,離子化閤物Al2Au4和BAlAu4.採用密度汎函和波函數理論方法對比研究瞭缺電子體繫B2Au4、Al2Au4和BAlAu4的幾何和電子結構.詳細討論瞭它們基態結構的軌道、適應性自然密度劃分(AdNDP)和電子跼域函數(ELF)分析.計算結果錶明稍微扭麯變形的C2 B2Au4是基態結構,在這箇共價化閤物中含有兩箇B―Au―B三中心二電子(3c-2e)鍵.然而C3v Al+(AlAu4)-和C3v Al+(BAu4)-被研究證明是含有三箇X―Au―Al三中心二電子鍵的類鹽化閤物(在Al2Au4中X=Al, BAlAu4中X=B). Al2Au4和BAlAu4是至今為止首例報道的在離子缺電子體繫中含有金橋鍵的化閤物.同時計算瞭B2Au4-、Al2Au4-和BAlAu4-陰離子基態結構的絕熱剝離能和垂直剝離能,為實驗錶徵提供依據.文中報道的金橋鍵為共價鍵和離子鍵相結閤的缺電子體繫提供瞭一箇有趣的鍵閤模式,有助于設計含有高度分散金原子的新材料和催化劑.
Au/H상사성적연구시현대화학중적일개열문화제.아문종이론상보도Au/H상사적신성원：공개화합물B2Au4,리자화합물Al2Au4화BAlAu4.채용밀도범함화파함수이론방법대비연구료결전자체계B2Au4、Al2Au4화BAlAu4적궤하화전자결구.상세토론료타문기태결구적궤도、괄응성자연밀도화분(AdNDP)화전자국역함수(ELF)분석.계산결과표명초미뉴곡변형적C2 B2Au4시기태결구,재저개공개화합물중함유량개B―Au―B삼중심이전자(3c-2e)건.연이C3v Al+(AlAu4)-화C3v Al+(BAu4)-피연구증명시함유삼개X―Au―Al삼중심이전자건적류염화합물(재Al2Au4중X=Al, BAlAu4중X=B). Al2Au4화BAlAu4시지금위지수례보도적재리자결전자체계중함유금교건적화합물.동시계산료B2Au4-、Al2Au4-화BAlAu4-음리자기태결구적절열박리능화수직박리능,위실험표정제공의거.문중보도적금교건위공개건화리자건상결합적결전자체계제공료일개유취적건합모식,유조우설계함유고도분산금원자적신재료화최화제.
Au/H similarity is a hot topic in chemistry. Here, we report the theoretical prediction of new members of the Au/H analogy family:covalent B2Au4, ionic Al2Au4, and BAlAu4. A comparative study of the geometric and electronic structures of electron-deficient B2Au4, Al2Au4, and BAlAu4 was performed based on density and wave functional theories. Detailed orbital analyses, adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses were performed. Ab initio theoretical evidence strongly suggests that the ground state of slightly distorted C2 B2Au4 is a covalent complex containing two B―Au―B three centers-two electrons (3c-2e) bonds. Unexpectedly, C3v Al+(AlAu4)-and C3v Al+(BAu4)-are predicted to have a salt-like composition with three X―Au―Al 3c-2e bonds (X=Al in Al2Au4, X=B in BAlAu4). Al2Au4 and BAlAu4 represent the first examples of bridging gold bonds in ionic-deficient systems. The adiabatic and vertical detachment energies of the anions were calculated to facilitate their future experimental characterization. Bridging gold addressed in this work provides an interesting bonding mode for covalent and ionic-deficient systems, and may aid in designing new materials and catalysts with highly dispersed Au atoms.
