10.1021/jp100723p.s001 Giacomo Miceli Giacomo Miceli Clotilde S. Cucinotta Clotilde S. Cucinotta Marco Bernasconi Marco Bernasconi Michele Parrinello Michele Parrinello First Principles Study of the LiNH<sub>2</sub>/Li<sub>2</sub>NH Transformation American Chemical Society 2010 ab initio simulations LiNH 2 LiNH 2 crystallites NH 3 desorption First Principles Study Li 2NH 2010-09-09 00:00:00 Journal contribution https://acs.figshare.com/articles/journal_contribution/First_Principles_Study_of_the_LiNH_sub_2_sub_Li_sub_2_sub_NH_Transformation/2732146 On the basis of ab initio simulations, we propose a scenario for the decomposition pathway of Li amide into Li imide and ammonia (2LiNH<sub>2</sub> → Li<sub>2</sub>NH + NH<sub>3</sub>) which represents the first step of the dehydrogenation reaction of the LiNH<sub>2</sub>/LiH<sub>3</sub> mixture. Activation energies for formation of NH<sub>3</sub> in LiNH<sub>2</sub>, for diffusion of charged species (H<sup>+</sup>, Li<sup>+</sup>) in LiNH<sub>2</sub> and Li<sub>2</sub>NH, for H<sup>+</sup>/Li<sup>+</sup> transfer across the LiNH<sub>2</sub>/Li<sub>2</sub>NH interface and for NH<sub>3</sub> desorption at the surface of LiNH<sub>2</sub> and Li<sub>2</sub>NH have been computed from first principles. The results actually suggest that the transformation path depends on the surface-to-volume ratio of the LiNH<sub>2</sub> crystallites.