Journal of the American Chemical Society, Vol.138, No.9, 3218-3227, 2016
Fully Hydrogenated Beryllium Nanoclusters
We present the ground state and energetically low structures of BenH2n, nano clusters as predicted using density functional theory (DFT) and employing the M06 meta-hybrid exchange-correlation functional. Results using the M06 functional are benchmarked against high accuracy coupled-cluster CCSD(T) and found to be in excellent agreement. For small values of n, the linear or polymeric form is the lowest energy geometry, while for sizes larger, n > 9 ring type and link type structures are the energetically lowest configurations. This trend has also been observed through ab initio molecular dynamics (AIMD) simulations at finite temperatures. In addition to the binding energies of the structures we report on polymerization energies, Be-H bond energies with respect to coordination details, hydrogen desorption energies of saturated and oversaturated species, as well as computed infrared spectra of all the ground presented. Furthermore, we find that the saturated polymeric forms of the nanoclusters state and energetically low lying structures cannot retain molecular hydrogen, in contrast to what is expected when zero point energy corrections are not taken into account.