RESUMEN
The study of C2 Al4 -/0 and C2 Al5 -/0 was conducted using anion photoelectron spectroscopy and quantum chemical computations. The present findings reveal that C2 Al4 - has a boat-like structure, with a single C2 unit surrounded by four aluminum atoms. In contrast, the neutral C2 Al4 species adopts a D2h planar structure with two planar tetracoordinate carbon (ptC) units, consistent with previous reports. Furthermore, the global minimum isomer of C2 Al5 - adopts a D3h symmetry, where the C2 unit interacts with five aluminum atoms. It was also found that a lower symmetry structure of C2 Al5 - , where all five aluminum atoms are located on the same side of the C2 unit, albeit slightly higher in energy compared to the D3h structure. These computations show that the D3h structure of C2 Al5 - is highly stable, exhibiting a large HOMO-LUMO gap.
RESUMEN
Carbon-doped aluminum cluster anions, AlnC- (n = 6-15), were generated by laser vaporization and investigated by mass-selected anion photoelectron spectroscopy. The geometric structures of AlnC- (n = 6-15) anions were determined by the comparison of theoretical calculations with the experimental results. It is found that the most stable structure of Al6C- is a carbon endohedral triangular prism. The Al7C- anion is a magic cluster with high stability. The structures of Al7-9C- can be viewed as the additional aluminum atoms attached around the triangular prism Al6C-. Two isomers of Al10C- have been detected in the experiments. The most stable one has a planar tetracoordinate carbon structure. The second one derives from Al9C- with the carbon atom located in a pentagonal bipyramid. The Al11C- anion has a bilayer structure composed of one planar tetracoordinate carbon and one aluminum-centered hexagon, in which the major interactions between two layers are multicenter bonds. The structures of Al12-14C- can be viewed as evolving from Al11C- by adding aluminum atoms to interact with the carbon atom. In Al15C-, the carbon atom stays at the surface with a tetracoordinate structure, and an icosahedral Al13 unit can be identified as a part of the geometric structure of Al15C-.
RESUMEN
The AlnC5- (n = 1-5) clusters were detected in the gas-phase and were investigated via mass-selected anion photoelectron spectroscopy. The structures of AlnC5-/0 (n = 1-5) were explored by theoretical calculations. It is found that the structures of AlC5-/0 and Al2C5-/0 are linear while those of Al3C5-/0, Al4C5-/0, and Al5C5-/0 are two-dimensional. The most stable structures of AlC5-/0 and Al2C5-/0 are linear with the Al atoms attached to the ends of C5 chain. The most stable structures of Al3C5-/0 can be viewed as three Al atoms interacting with a nonlinear C5 chain. The most stable structure of Al4C5- anion is a planar structure composed of a C2 unit, a C3 unit, and two Al2 units, while that of the neutral Al4C5 cluster has four Al atoms connected to different positions of a distorted C5 chain. The global minimum structures of Al5C5-/0 are planar structures composed of an Al4C quadrilateral, two C2 groups, and an Al atom connected to two C2 groups. Planar tetracoordinate carbon (ptC) has been identified in the structures of both anionic and neutral Al5C5. It is worth mentioning that the star-like structure of Al5C5- is slightly higher in energy than the ground state structure. The comparison of theoretical calculations with the experimental spectra indicates the star-like structure of Al5C5- may also appear in our experiments.
RESUMEN
Anion photoelectron spectroscopy and theoretical calculations were used to investigate the structural and bonding properties of Al4C6-/0 clusters. The vertical detachment energy of Al4C6- was measured to be 3.36 ± 0.08 eV. The structure of the Al4C6- anion is confirmed to be a bowl-shaped distorted triangle with an Al atom at the center and three Al atoms at the vertices. The global minimum isomer of neutral Al4C6 has a planar triangle-shaped structure with D3h symmetry. Both anionic and neutral Al4C6 have a hexacoordinated Al atom surrounded by three C≡C groups. Compared with the structure of neutral Al4C6, the structure of Al4C6- is distorted due to the addition of the excess electron. The molecular orbital analysis shows that the singly occupied molecular orbital of Al4C6- mainly locates on one side of the triangle plane and the neutral Al4C6 has a large highest occupied molecular orbital and lowest unoccupied molecular orbital gap. Theoretical calculations indicate that neutral Al4C6 has some aromaticity.
RESUMEN
The structural and electronic properties of MnCn - (n = 3-10) clusters have been investigated using size-selected photoelectron spectroscopy and density functional theory calculations. The vertical detachment energies of MnCn - exhibit a strong odd-even alternation with increasing number of carbon atoms: the vertical detachment energies of MnCn - containing even number of carbon atoms are higher than those of adjacent ones containing odd number of carbon atoms. The theoretical analyses indicate that the spin multiplicities and relative stabilities of MnCn -/0 also exhibit odd-even alternations. It is found that MnC3 - has three degenerate isomers with two linear structures in different electronic states and one fanlike structure. For n = 4-6, 8, and 10, the ground state structures are all linear with the Mn atom at one end. MnC7 - and MnC9 - have cyclic structures. As for the neutral species, MnC3 and MnC4 adopt fan-shaped structures, MnC5 has a linear structure, and MnC6-10 have cyclic configurations. The atomic dipole moment corrected Hirshfeld population analysis shows that the electrons transfer from the Mn atom to the Cn units. The total spin magnetic moments of MnCn -/0 (n = 3-10) clusters are mainly contributed by the local magnetic moments on the Mn atom.