Clusters electronic configuration

This example shows that it is incorrect to use unchanged cluster electronic configurations in chemisorption calculations. Most importantly, however, it shows that a gratifyingly similar picture of the importance of such effects as (relieve of) Pauli repulsion, configuration changes, polarization of the metal substrate, etc. emerge from such different electronic structure methods as Hartree-Fock and X (LSD). 

In coating fullerenes with alkali metals, the stability of the cluster seemed to be determined primarily by the electronic configuration. The units C qM and C7oMg, where M is any alkali metal, proved to be exceptionally stable cluster building blocks. Coating a fullerene with more than 7 alkali metal atoms led to an even-odd alternation in the mass spectra, inter-... 

Figure 2.14. The molecular orbitals of gas phase carbon monoxide, (a) Energy diagram indicating how the molecular orbitals arise from the combination of atomic orbitals of carbon (C) and oxygen (O). Conventional arrows are used to indicate the spin orientations of electrons in the occupied orbitals. Asterisks denote antibonding molecular orbitals, (b) Spatial distributions of key orbitals involved in the chemisorption of carbon monoxide. Barring indicates empty orbitals.5 (c) Electronic configurations of CO and NO in vacuum as compared to the density of states of a Pt(lll) cluster.11 Reprinted from ref. 11 with permission from Elsevier Science.

In contrast to chloride compounds, niobium oxides have a VEC of 14 electrons, due to an overall anti-bonding character of the a2u state, caused by a stronger Nb-O anti-bonding contribution. In some cases, the VEC cannot be determined unambiguously due to the uncertainty in the electron distribution between the clusters and additional niobium atoms present in the majority of the structures. The 14-electron compounds exhibit semiconducting properties and weak temperature-independent paramagnetism. Unlike niobium chlorides, the oxides do not exhibit a correlation between the electronic configuration and intra-cluster bond distances. 

Slovokhotov, Yu.L. and Struchkov, Yu.T (1984) X-ray crystal structure of a distorted tetrahedral cluster in the salt [(Ph P)4Au4N] BF4 . Geometrical indication of stable electronic configurations in post-transition metal complexes and the magic number 18-e in centred gold clusters. Journal of Organometallic Chemistry, 177, 143-146. 

The 2 1 species are known as cuprates and are the most common synthetic reagents. Disubstituted Cu(I) species have the 3c 10 electronic configuration and would be expected to have linear geometry. The Cu is a center of high electron density and nucleophilicity, and in solution, lithium dimethylcuprate exists as a dimer [LiCu(CH3)2]2.3 The compound is often represented as four methyl groups attached to a tetrahedral cluster of lithium and copper atoms. However, in the presence of Lil, the compound seems to be a monomer of composition (CH3)2CuLi.4... 

Figure 2.4. Survey of the structures of TMI hosted in various zeolite- and silica-derived clusters as a function of the electron configuration obtained by VWN/DNP method (after [37]).

Binuclear Technetium Cluster Compounds with the d4-d4 Electronic Configuration of the Core Atoms... 

Interestingly, compounds of Class A or Class B have 50 cluster valence electrons if the three metal atoms are individually to have 18-electron configurations. Several of the compounds meet this requirement, e.g. (25), (27), (31) (34) or (36). However, compound (23) with 46 clusterValence ... 

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