Electronic and Hydrogen Storage Properties of Li-Terminated Linear Boron Chains Studied by TAO-DFT.

It has been extremely difficult for conventional computational approaches to reliably predict the properties of multi-reference systems (i.e., systems possessing radical character) at the nanoscale. To resolve this, we employ thermally-assisted-occupation density functional theory (TAO-DFT) to predict the electronic and hydrogen storage properties of Li-terminated linear boron chains (Li2Bn), with n boron atoms (n = 6, 8, …, and 16). From our TAO-DFT results, Li2Bn, which possess radical character, can bind up to 4 H2 molecules per Li, with the binding energies in the desirable regime (between 20 and 40 kJ/mol per H2). The hydrogen gravimetric storage capacities of Li2Bn range from 7.9 to 17.0 wt%, achieving the ultimate goal of the United States Department of Energy. Accordingly, Li2Bn could be promising media for storing and releasing H2 at temperatures much higher than the boiling point of liquid nitrogen.