Exploring the Structure and Bonding of Group 13 Homogeneous and Heterogeneous Hydrides with the X2H4 Stoichiometry: A Theoretical Investigation

We investigated the structure evolution of the Group 13 hydrides on the example of X2H4 (X = B, Al, Ga, In, Tl) and BAlH4, AlGaH4, GaInH4, and InTlH4 stoichiometries via density functional theory (DFT) and ab initio quantum chemistry methods performing Coalescence Kick (CK) global minimum search and AdNDP chemical bonding analysis. We found that all global minimum structures possess multicenter electron bonds. The difference between the structures of X2H4 stoichiometry for boron and aluminum is much more significant than that between other pairs of Al–Ga, Ga–In, and In–Tl. The evolution of Group 13 hydride structure involves the gradual prevalence of classical 2c-2e bonds over multicenter bonds for heavier elements. The found structural features of the heterogeneous hydrides are in total agreement with those of homogeneous hydrides and with the trends common for the periodic table that allows us to investigate the structural evolution of Group 13 hydrides more completely.