On Three-Electron Bonds and Hydrogen Bonds in the Open-Shell Complexes [H2X2]+ for X = F, Cl, and Br†

The [H2X2]+ (X = Cl, Br) formula could refer to two possible stable structures, namely, the hydrogen-bonded complex and the three-electron-bonded one. In contrary to the results published by other authors, we claim that for the F-type structures the hydrogen-bonded form is the only possible one and the [HFFH]+ complex is an artifact as its wave function is unstable. For all analyzed molecules, the IR anharmonic spectra have been simulated, which enabled a deeper analysis of other authors' published results of IR low-temperature matrix experiments. Topological atoms in molecules and electron localization function investigations have revealed that the nature of the bond in three-electron-bonded structures is similar to the covalent-depleted one in F2 or HOO molecules, but the effect of removing electrons from the bond area is stronger.

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