H₂Adsorption in a Porous Crystal: Accurate First-Principles Quantum Simulation

Abstract

A general method is presented for constructing, from ab initio quantum chemistry calculations, the potential energy surface (PES) for H2 absorbed in a porous crystalline material. The method is illustrated for the metal-organic framework material MOF-5. Rigid body quantum diffusion Monte Carlo simulations are used in the construction of the PES and to evaluate the quantum ground state of H2 in MOF-5, the zero-point energy, and the enthalpy of adsorption at 0 K.

Can Systematic Molecular Fragmentation Be Applied to Direct Ab Initio Molecular Dynamics?

“…55 Adsorption of H 2 in a metal−organic-framework material has also been studied with quantum diffusion Monte Carlo using a fragment-based global PES of this type. 56 However, in this case the PES was only a function of six coordinates. In the case of hydrogen reacting with a hydrogen covered silicon surface, the largest fragment contained nine atoms.…”

“…Classical simulations of reactive scattering of a hydrogen atom from a hydrogen covered Silicon crystal surface has been reported . Adsorption of H 2 in a metal–organic-framework material has also been studied with quantum diffusion Monte Carlo using a fragment-based global PES of this type . However, in this case the PES was only a function of six coordinates.…”

Interpolating DFT Data for 15D Modeling of Methane Dissociation on an fcc Metal

“…Reactions with a high coverage of an intermediate state cannot yet be described with the correct treatment of the symmetry of the surface. The formalism for describing the plane‐group‐symmetric PES of an adsorbate interacting with a crystalline surface can be generalized in a straight‐forward manner to describe the interaction of an adsorbate interacting with a rigid lattice in three dimensions, with full space group symmetry .…”