화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.122, No.10, 2792-2800, 2018
Physisorption of H-2 on Fullerenes and the Solvation of C-60 by Hydrogen Clusters at Finite Temperature: A Theoretical Assessment
The interaction between hydrogen and carbonaceous nanostructures is of fundamental interest in various areas of physical chemistry. In this contribution we have revisited the physisorption of hydrogen molecules and H-2 clusters on fullerenes, following a first-principles approach in which the interaction is quantitatively evaluated for the C-20 system using high-level electronic structure methods. Relative to coupled cluster data at the level of single, double, and perturbative triple excitations taken as a benchmark, the results for rotationally averaged physisorbed H-2 show a good performance of MP2 variants and symmetry-adapted perturbation theory, but significant deviations and basis set convergence issues are found for dispersion-corrected density functional theory. These electronic structure data are fitted to produce effective coarse-grained potentials for use in larger systems such as C-60-H-2. Using path-integral molecular dynamics, the potentials are also applied to parahydrogen clusters solvated around fullerenes, across the regime where the first solvation shell becomes complete and as a function of increasing temperature. For C-60 our findings indicate a sensible dependence of the critical solvation size on the underlying potential. As the temperature is increased, a competition is found between the surface and radial expansions of the solvation shell, with one molecule popping away at intermediate temperatures but getting reinserted at even higher temperatures.