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@article{1458897,
author = {Danovich, David and Foroutannejad, Cina and Hiberty, Philippe C and Shaik, Sason},
article_location = {WASHINGTON},
article_number = {7},
doi = {http://dx.doi.org/10.1021/acs.jpca.7b11919},
keywords = {three-electron bond; Valence Bond Theory; Quantum Theory of Atoms in Molecules; MR-SCF Computations},
language = {eng},
issn = {1089-5639},
journal = {Journal of Physical Chemistry A},
title = {Nature of the Three-Electron Bond},
url = {https://pubs.acs.org/doi/10.1021/acs.jpca.7b11919},
volume = {122},
year = {2018}
}
TY - JOUR
ID - 1458897
AU - Danovich, David - Foroutannejad, Cina - Hiberty, Philippe C - Shaik, Sason
PY - 2018
TI - Nature of the Three-Electron Bond
JF - Journal of Physical Chemistry A
VL - 122
IS - 7
SP - 1873-1885
EP - 1873-1885
PB - AMER CHEMICAL SOC
SN - 10895639
KW - three-electron bond
KW - Valence Bond Theory
KW - Quantum Theory of Atoms in Molecules
KW - MR-SCF Computations
UR - https://pubs.acs.org/doi/10.1021/acs.jpca.7b11919
L2 - https://pubs.acs.org/doi/10.1021/acs.jpca.7b11919
N2 - We analyze the properties of 15 3-electron bonds, which include sigma-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, pi-3-electron-bonds as in hydrazine radical cations, and doubly-pi-(3e)-bonded species such as O-2, FeO+, S-2, etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RECS) of the three electrons, and the bond dissociation energies (De). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian (L) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such as F-2 or the central bond in [1.1.1]propellane, here too L is positive, thus showing the excess kinetic energy of the shared density due to the Pauli repulsion in the 3-electron VB structures. The RECS values for 3-electron bonds are invariably larger than the corresponding bond energies. For the doubly-pi-(3e) -bonded species, RECS is very large, exceeding 100 kcal mol(-1). As such, it is fitting to conclude that sigma- and pi-3-electron-bonds find their natural place in the CSB family along with two-electron CSBs, with which they share identical energetic and topological characteristics. Experimental manifestations/tests of 3e-CSBs are proposed.
ER -
DANOVICH, David, Cina FOROUTANNEJAD, Philippe C HIBERTY a Sason SHAIK. Nature of the Three-Electron Bond. \textit{Journal of Physical Chemistry A}. WASHINGTON: AMER CHEMICAL SOC, 2018, roč.~122, č.~7, s.~1873-1885. ISSN~1089-5639. Dostupné z: https://dx.doi.org/10.1021/acs.jpca.7b11919.
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