Quantum dynamics of hydrogen interacting with single-walled carbon nanotubes: multiple H-atom adsorbates

In a previous paper J. L. McAfee and B. Poirier, J. Chem. Phys. 130, 064701 (2009)], using spin-polarized density functional theory (DFT), the authors reported a binding energy of 0.755 eV, for a single hydrogen atom adsorbed on a pristine (unrelaxed) (5,5) single-walled carbon nanotube (SWNT) substrate. A full three-dimensional (3D) potential energy surface (PES) for the SWNT-H system was also developed, and used in a quantum dynamics calculation to compute all rovibrational bound states, and associated equatorial and longitudinal adsorbate migration rates. A highly pronounced preference for the latter migration pathway at ambient temperatures was observed. In this work, we extend the aforementioned study to include multiple H-atom adsorbates. Extensive DFT calculations are performed, in order to ascertain the most relevant dynamical pathways. For two adsorbates, the SWNT-H-H system is found to exhibit highly site-specific binding, as well as long-range correlation and pronounced binding energy enhancement. The latter effect is even more pronounced in the full-hydrogenation limit, increasing the per-adsorbate binding energy to 2.6 eV. To study migration dynamics, a single-hole model is developed, for which the binding energy drops to 2.11 eV. A global 3D PES is developed for the hole migration model, using 40 radial × 18 cylindrical ab initio geometries, fit to a Fourier basis with radially dependent expansion coefficients (rms error 4.9 meV). As compared with the single-adsorbate case, the hole migration PES does not exhibit separate chemisorption and physisorption wells. The barrier to longitudinal migration is also found to be much lower. Quantum dynamics calculations for all rovibrational states are then performed (using a mixed spectral basis/phase-space optimized discrete variable representation), and used to compute longitudinal migration rates. Ramifications for the use of SWNTs as potential hydrogen storage materials are discussed.