Quadruple chemical bonding in the diatomic anions TcN−, RuC−, RhB−, and PdBe−. Issue 16 (14th April 2021)

• Record Type: Journal Article
• Authors: Tzeli, Demeter
• Is Part Of: Journal of computational chemistry. Volume 42:Issue 16(2021)
• Page Start: 1126
• Page End: 1137
• Publication Date: 2021-04-14
• Subjects: coupled cluster calculations -- multireference calculations -- PdBe− -- quadruple bonding -- RhB− -- RuC− -- TcN−; Chemistry -- Data processing -- Periodicals; 542.85
• DOI: 10.1002/jcc.26527
• Languages: English
• ISSNs: 0192-8651

Abstract

Abstract: Quadruple bonding is uncommon for main group elements and the identification of species forming such bonds is remarkably interesting particularly in diatomic anions for which there is a lack of information. Here, it is found that the MX − anions, TcN −, RuC −, RhB −, and PdBe −, present quadruple bonding, as do the corresponding MX neutrals, even though a different type of σ 2 bond is involved in ∑ + states of neutral and anions. Specifically, the ground states ( X 2 Δ or X 2 ∑ + ) of the four anions and their first excited states ( A 2 ∑ + or A 2 Δ) of TcN −, RuC −, and RhB − present quadruple bonds consisting of two σ and two π bonds: (4dz2 − 2pz ) 2, 5pz 0 ← 2s 2, (4dxz − 2px ) 2, and (4dyz − 2py ) 2 . Bond lengths, dissociation energies, spectroscopic data and electron affinities were calculated via high‐level multireference and coupled‐cluster methodology using the aug–cc–pV5ZX (‐PP)M basis set. Strong bonding results in short bond lengths ranging from 1.602 (TcN − ) to 1.944 (PdBe − ) Å. Adiabatic (diabatic) binding energies reach up to 139 (184) kcal/mol. Electron affinities (EA) were calculated at 1.368 (TcN), 1.242 (RuC), 0.873 (RhB), 0.743 (PdBe) eV. Only for RhB has EA been measured experimentally at 0.961 eV, in good agreement with the value reported here. Abstract : Analysis of the chemical bonding is a very fundamental aspect of chemistry. Quadruple bonding is uncommon for main group elements and the identification of species forming such bonds is remarkably interesting. Four MX − anions, TcN −, RuC −, RhB −, PdBe −, present quadruple bonding (1σ 2 2σ 2 1π 2 2π 2 ) in their ground and in the first excited states of TcN −, RuC −, RhB − . Spectroscopic data, binding energies and electron affinities were calculated via high‐level multireference and coupled‐cluster methodology.