Abstract Density functional theory and ab initio multi-reference calculations are performed to examine the stability and electronic structure of boron complexes that host diffuse electrons in their periphery. Such complexes (solvated electron precursors or SEPs) have been experimentally identified and studied theoretically for several s- and d-block metals. For the first time, we demonstrate that a p-block metalloid element can form a stable SEP when appropriate ligands are chosen. We show that three ammonia and one methyl ligands can displace two of the three boron valence electrons to a peripheral 1s-type orbital. The shell model for these outer electrons is identical to previous SEP systems (1s, 1p, 1d, 2s). Further, we preformed the first examination of a molecular system consisting of two SEPs bridged by a hydrocarbon chain. The electronic structure of these dimers is very similar to that of traditional diatomic molecules forming bonding and anti-bonding σ and π orbitals. Their ground state electronic structure resembles that of two He atoms, and our results indicate that the excitation energies are nearly independent of the chain length for four carbon atoms or longer. These findings pave the way for the development of novel materials similar to expanded metals and electrides.
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Ground and excited states analysis of alkali metal ethylenediamine and crown ether complexes
High-level electronic structure calculations are carried out to obtain optimized geometries and excitation energies of neutral lithium, sodium, and potassium complexes with two ethylenediamine and one or two crown ether molecules. Three different sizes of crowns are employed (12-crown-4, 15-crown-5, 18-crown-6). The ground state of all complexes contains an electron in an s-type orbital. For the mono-crown ether complexes, this orbital is the polarized valence s-orbital of the metal, but for the other systems this orbital is a peripheral diffuse orbital. The nature of the low-lying electronic states is found to be different for each of these species. Specifically, the metal ethylenediamine complexes follow the previously discovered shell model of metal ammonia complexes (1s, 1p, 1d, 2s, 1f), but both mono- and sandwich di-crown ether complexes bear a different shell model partially due to their lower (cylindrical) symmetry and the stabilization of the 2s-type orbital. Li(15-crown-5) is the only complex with the metal in the middle of the crown ether and adopts closely the shell model of metal ammonia complexes. Our findings suggest that the electronic band structure of electrides (metal crown ether sandwich aggregates) and expanded metals (metal ammonia aggregates) should be different despite the similar nature of these systems (bearing diffuse electrons around a metal complex).
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- Award ID(s):
- 1940456
- NSF-PAR ID:
- 10329570
- Date Published:
- Journal Name:
- Physical Chemistry Chemical Physics
- Volume:
- 23
- Issue:
- 36
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 20298 to 20306
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D1CP02552J
