Journal ArticleDOI
Probing the Electronic Structure and Aromaticity of Pentapnictogen Cluster Anions Pn5- (Pn = P, As, Sb, and Bi) Using Photoelectron Spectroscopy and ab Initio Calculations
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In this article, the electronic structure and chemical bonding of the pentapnictogen cluster anions, Pn5- (Pn = P, As, Sb, and Bi), were investigated using both photoelectron spectroscopy and ab initio calculations.Abstract:
The electronic structure and chemical bonding of the pentapnictogen cluster anions, Pn5- (Pn = P, As, Sb, and Bi), were investigated using both photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra were obtained for the anions at several photon energies and were analyzed according to the theoretical calculations. The ground state of all the Pn5- species was found to be the aromatic cyclic D5h structure with a C2v low-lying isomer. We found that the C2v isomer gains stability from P5- to Sb5-, consistent with the experimental observation of the coexistence of both isomers in the spectra of Sb5-. The valence molecular orbitals (MOs) of the D5h Pn5- were analyzed and compared to those of the aromatic C5H5- hydrocarbon. The same set of π-MOs is shown to be occupied in the D5h Pn5- and C5H5- species, except that the MO ordering is slightly different. Whereas the three π-MOs in C5H5- all lie above the σ-MOs, the third π orbital (1a2‘ ‘ in Pn5-) lies below the σ-MOs. The stab...read more
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Journal ArticleDOI
All-Metal Aromaticity and Antiaromaticity
TL;DR: These new developments have shown that aromaticity and antiaromaticity in metal systems have frequently multiple nature, being o-aromatic/antiaromatic and n-Aromatic/Antiaromatic, which is not found in organic aromatic/antaromatic molecules.
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DFT study of “all-metal” aromatic compounds
TL;DR: An overview of recent quantum chemical studies on all-metal aromatic compounds is presented in this paper, where the mechanistic insight gained for the aromatic character of all metal aromatic molecules is discussed and the predictive nature of the electronic structure calculation methods particularly those based on density functional theory (DFT).
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A Critical Assessment of the Performance of Magnetic and Electronic Indices of Aromaticity
TL;DR: Evaluating the aromaticity of two series of all-metal and semimetal clusters with predictable aromaticity trends by means of NICS and MCI shows that the expected trends are generally better reproduced by MCI than NICS.
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Reactivity, Selectivity, and Aromaticity of Be32- and Its Complexes
TL;DR: The stability, reactivity, and aromaticity of the Be32- dianion and its bimetallic species are investigated, and the recently discovered direct Zn-Zn bond is stabilized through the complexation with Be32-, and a new compound is reported.
Book ChapterDOI
Aromatic Phosphorus Heterocycles
L. Nyulászi,Zoltán Benkő +1 more
TL;DR: In this paper, it is shown that even small effects can have a large impact on the chemistry of these compounds and the analysis of subtle changes in aromaticity can be of importance in the future.
References
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K. D. Dobbs,Warren J. Hehre +1 more
TL;DR: In this paper, a series of efficient split-valence basis sets for first-row transition metals, termed 3-21G, has been constructed based on previously-formulated minimal expansions of Huzinaga, in which each atomic orbital has been represented by a sum of three gaussians.
Journal ArticleDOI
Photoelectron spectroscopy of size‐selected transition metal clusters: Fe−n, n=3–24
TL;DR: In this article, a higher resolution magnetic bottle photoelectron spectrometer for the study of the electronic structure of size-selected metal clusters is presented, and the initial study on Fe−n (n=3−24) is reported at a photon energy of 3.49 eV.
Journal ArticleDOI
Generation of Metal Clusters Containing from 2 to 500 Atoms
TL;DR: In this paper, the main problems underlying the experimental study of particles with sizes between single atoms and the solid state have been solved: the formation of metal clusters, their individual detection, and the separation of beams with uniform cluster size.
Journal ArticleDOI
Semidirect algorithms for third-order electron propagator calculations
TL;DR: In this paper, an efficient procedure for third-order electron propagator calculations of ionization energies and electron affinities is reported, and an integral transformation program for direct and semidirect algorithms is modified to store only nonzero integrals according to Abelian point group symmetry.
Journal ArticleDOI
Complexes with Substituent-free Acyclic and Cyclic Phosphorus, Arsenic, Antimony, and Bismuth Ligands
TL;DR: In this article, the phosphorus, arsenic, antimony and bismuth ligands were nearly always understood to be molecules such as R3E, R2E(CH2)nER2, and RC[(CH 2 nER2]3(E = P, As, Sb, Bi) in which the lone pair of the atom E functions as a 2e donor.