Investigating the structures and properties of Au-Ge mixed clusters can give insight into the microscopic mechanisms in gold-catalyzed Ge films and can also provide valuable information for the production of germanium...Investigating the structures and properties of Au-Ge mixed clusters can give insight into the microscopic mechanisms in gold-catalyzed Ge films and can also provide valuable information for the production of germanium-based functional materials. In this work, size-selected anion photoelectron spectroscopy and theoretical calculations were used to explore the structural evolution and electronic properties of Au2Gen^-/0 (n=1-8) clusters. It is found that the two Au atoms in Au2Gen^-/0 (n=1-8) showed high coordination numbers and weak aurophilic interactions. The global minima of Au2Gen- anions and Au2Gen neutrals are in spin doublet and singlet states, respectively. Au2Gen- anions and Au2Gen neutrals showed similar structural features, except for Au2Ge4^-/0 and Au2Ge5^-/0. The C2v symmetric V-shaped structure is observed for Au2Ge1^-/0, while Au2Ge2^-/0 has a C2v symmetric dibridged structure. Au2Ge3^-/0 can be viewed as the two Au atoms attached to different Ge-Ge bonds of Ge3 triangle. Au2Ge4- has two Au atoms edge-capping Ge4 tetrahedron, while Au2Ge4 neutral adopts a C2v symmetric double Au atoms face-capping Ge4 rhombus. Au2Ge5-8^-/0 show triangular, tetragonal, and pentagonal prism-based geometries. Au2Ge6 adopts a C2v symmetric tetragonal prism structure and exhibits σ plus π double bonding characters.展开更多
We measured the photoelectron spectra of AuC_(n)^(-)(n=3-8)and conducted theoretical study on the structures and properties of AuC_(n)^(-/0)(n=3-8).It is found that the photoelectron spectra of AuC_(n)^(-)exhibit odd-...We measured the photoelectron spectra of AuC_(n)^(-)(n=3-8)and conducted theoretical study on the structures and properties of AuC_(n)^(-/0)(n=3-8).It is found that the photoelectron spectra of AuC_(n)^(-)exhibit odd-even alternation.The spectral features of AuC_(3)^(-),AuC_(5)^(-),and AuC_(7)^(-)are much broader than those of AuC_(4)^(-),AuC_(6)^(-),and AuC_(5)^(-).The vertical detachment energies of AuC_(3)^(-),AuC_(5)^(-),and AuC_(7)^(-)are lower than those of AuC_(4)^(-),AuC_(6)^(-),and AuCs_(8)^(-).The most stable structures of AuC_(n)^(-)(n=3-8)are chain structures.The most stable structures of neutral AuC_(n)(n=3-8)are linear structures except that those of AuC_(3) and AuC_(5) are slightly bent.The calculated∠AuCC angles,Au-C bond lengths,and the charges on Au atom also show odd-even alternations,consistent with the experimental observations.展开更多
We measured the photoelectron spectra of Al_(n)C_(4)^(−)(n=2−4)clusters by using size-selected anion photoelectron spectroscopy.The structures of Al_(n)C_(4)^(−/0)(n=2−4)clusters were explored with quantum chemistry c...We measured the photoelectron spectra of Al_(n)C_(4)^(−)(n=2−4)clusters by using size-selected anion photoelectron spectroscopy.The structures of Al_(n)C_(4)^(−/0)(n=2−4)clusters were explored with quantum chemistry calculations and were determined by comparing the theoretical results with the experimental spectra.It is found that the most stable structure of Al_(2)C_(4)^(−) anion is a C_(2v)symmetry planar structure with two Al atoms interacting with two C_(2)units.In addition,Al_(2)C_(4)^(−) anion also has a D∞h symmetry linear structure with two Al atoms located at the two ends of a C_(4)chain,which is slightly higher in energy than the planar structure.The most stable structure of neutral Al_(2)C_(4)has a D∞h symmetry linear structure.The most stable structure of Al_(3)C_(4)^(−) anion is a planar structure with three Al atoms interacting with two C_(2)units.Whereas neutral Al_(3)C_(4)cluster has a C_(2v)symmetric V-shaped bent structure.The global minima structures of both Al_(4)C_(4)^(−) and neutral Al_(4)C_(4)are C_(2)h symmetry planar structures with four Al atoms interacting with the ends of two C_(2)units.Adaptive natural density partitioning analyses of Al_(n)C_(4)^(−)(n=2−4)clusters show that the interactions between the Al atoms and C_(2)units have bothσandπcharacters.展开更多
基金supported by the National Natural Science Foundation of China (No.21273246 and No.21103202)the Chinese Academy of Sciences (No.QYZDB-SSW-SLH024)+3 种基金the Natural Science Foundation of Shandong Province of China (No.ZR2018BB040)Open Funds of Beijing National Laboratory for Molecular Sciences (No.BNLMS201804)Research Start-up Funds (Doctoral Science Foundation) of Heze University (No.XY18BS02)Chinese Academy of Sciences President’s International Fellowship Initiative (PIFI) (No.2018VMA0011)
文摘Investigating the structures and properties of Au-Ge mixed clusters can give insight into the microscopic mechanisms in gold-catalyzed Ge films and can also provide valuable information for the production of germanium-based functional materials. In this work, size-selected anion photoelectron spectroscopy and theoretical calculations were used to explore the structural evolution and electronic properties of Au2Gen^-/0 (n=1-8) clusters. It is found that the two Au atoms in Au2Gen^-/0 (n=1-8) showed high coordination numbers and weak aurophilic interactions. The global minima of Au2Gen- anions and Au2Gen neutrals are in spin doublet and singlet states, respectively. Au2Gen- anions and Au2Gen neutrals showed similar structural features, except for Au2Ge4^-/0 and Au2Ge5^-/0. The C2v symmetric V-shaped structure is observed for Au2Ge1^-/0, while Au2Ge2^-/0 has a C2v symmetric dibridged structure. Au2Ge3^-/0 can be viewed as the two Au atoms attached to different Ge-Ge bonds of Ge3 triangle. Au2Ge4- has two Au atoms edge-capping Ge4 tetrahedron, while Au2Ge4 neutral adopts a C2v symmetric double Au atoms face-capping Ge4 rhombus. Au2Ge5-8^-/0 show triangular, tetragonal, and pentagonal prism-based geometries. Au2Ge6 adopts a C2v symmetric tetragonal prism structure and exhibits σ plus π double bonding characters.
基金supported by the Beijing Municipal Science&Technology Commission(No.Z191100007219009)。
文摘We measured the photoelectron spectra of AuC_(n)^(-)(n=3-8)and conducted theoretical study on the structures and properties of AuC_(n)^(-/0)(n=3-8).It is found that the photoelectron spectra of AuC_(n)^(-)exhibit odd-even alternation.The spectral features of AuC_(3)^(-),AuC_(5)^(-),and AuC_(7)^(-)are much broader than those of AuC_(4)^(-),AuC_(6)^(-),and AuC_(5)^(-).The vertical detachment energies of AuC_(3)^(-),AuC_(5)^(-),and AuC_(7)^(-)are lower than those of AuC_(4)^(-),AuC_(6)^(-),and AuCs_(8)^(-).The most stable structures of AuC_(n)^(-)(n=3-8)are chain structures.The most stable structures of neutral AuC_(n)(n=3-8)are linear structures except that those of AuC_(3) and AuC_(5) are slightly bent.The calculated∠AuCC angles,Au-C bond lengths,and the charges on Au atom also show odd-even alternations,consistent with the experimental observations.
基金supported by the Beijing Municipal Science&Technology Commission(No.Z191100007219009)the National Natural Science Foundation of China(No.21773255)。
文摘We measured the photoelectron spectra of Al_(n)C_(4)^(−)(n=2−4)clusters by using size-selected anion photoelectron spectroscopy.The structures of Al_(n)C_(4)^(−/0)(n=2−4)clusters were explored with quantum chemistry calculations and were determined by comparing the theoretical results with the experimental spectra.It is found that the most stable structure of Al_(2)C_(4)^(−) anion is a C_(2v)symmetry planar structure with two Al atoms interacting with two C_(2)units.In addition,Al_(2)C_(4)^(−) anion also has a D∞h symmetry linear structure with two Al atoms located at the two ends of a C_(4)chain,which is slightly higher in energy than the planar structure.The most stable structure of neutral Al_(2)C_(4)has a D∞h symmetry linear structure.The most stable structure of Al_(3)C_(4)^(−) anion is a planar structure with three Al atoms interacting with two C_(2)units.Whereas neutral Al_(3)C_(4)cluster has a C_(2v)symmetric V-shaped bent structure.The global minima structures of both Al_(4)C_(4)^(−) and neutral Al_(4)C_(4)are C_(2)h symmetry planar structures with four Al atoms interacting with the ends of two C_(2)units.Adaptive natural density partitioning analyses of Al_(n)C_(4)^(−)(n=2−4)clusters show that the interactions between the Al atoms and C_(2)units have bothσandπcharacters.
