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.
Original language | English |
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Article number | 015001 |
Journal | Electronic Structure |
Volume | 4 |
Issue number | 1 |
DOIs | |
State | Published - Mar 1 2022 |
Funding
The authors are indebted to Auburn University (AU) for financial support. EM is especially grateful to the donors of the James E Land endowment. This work was completed with resources provided by the Auburn University Easley Cluster. This material is based upon work supported by the National Science Foundation under Grant No. CHE-1940456. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation.
Keywords
- ammonia
- diffuse electrons
- excited states
- hydrogenic shell model
- solvated electron