Computational Investigation of Adsorption of Molecular Hydrogen on Lithium-Doped Corannulene

Abstract

Density functional theory and classical molecular dynamics simulations are used to investigate the prospect of lithium-doped corannulene as adsorbent material for H(2) gas. Potential energy surface scans at the level of B3LYP/6-311G(d,p) show an enhanced interaction of molecular hydrogen with lithium-atom-doped corannulene complexes with respect to that found in undoped corannulene. MP2(FC)/6-31G(d,p) optimizations of 4H(2)-(Li(2)-C(20)H(10)) yield H(2) binding energies of -1.48 kcal/mol for the H(2)-Li interaction and -0.92 kcal/mol for the H(2)-C interaction, whereas values of -0.94 and -0.83 kcal/mol were reported (J. Phys. Chem. B 2006, 110, 7688-7694) for physisorption of H(2) on the concave and the convex side of corannulene using MP2(full)/6-31G(d), respectively. Classical molecular dynamics simulations predict hydrogen uptakes in Li-doped corannulene assemblies that are significantly enhanced with respect to that found in undoped molecules, and the hydrogen uptake ability is dependent on the concentration of lithium dopant. For the Li(6)-C(20)H(10) complex, a hydrogen uptake of 4.58 wt % at 300 K and 230 bar is obtained when the adsorbent molecules are arranged in stack configurations separated by 6.5 A, and with interlayer distances of 10 A, hydrogen uptake reaches 6.5 wt % at 300 K and 215 bar.

DFT study on nonlinear optical properties of lithium-doped corannulene

“…The C−Li distances listed in Table 1 indicate that the location of the Li atom is close to the center of a six-membered ring. The binding energies of 1a and 1b are 69.7 and 74.1 kJ/mol, respectively, which is in good agreement with the results of Zhang et al [31]. The NBO charges on the Li atoms of 1a and 1b are 0.918 (e) and 0.942 (e), respectively, indicating charge transfer from Li to corannulene.…”

“…The molecule resembles a shallow bowl with C 5v symmetry ( Figure 1) and the six-membered rings at the periphery lie significantly out of the plane. C 20 H 10 exhibits a number of interesting properties [30,31] and its complexes with ions or atoms, such as alkaline cations or transition metal atoms [32][33][34][35], have been studied both experimentally and theoretically. Following the discussion above, we investigated corannulene molecules with Li doping for the design of novel NLO materials.…”

Buckybowls: Corannulene and Its Derivatives

“…Adsorption of hydrogen onto corannulene was theoretically studied by density functional theory (DFT) and molecular dynamic simulations, and also measured experimentally. [ 61,62 ] Experimentally hydrogen uptake of 0.8 mass% was obtained at ambient temperature (298 K) under the hydrogen pressure of 72 bar, which agreed well with molecular dynamic calculation. [ 61 ] Theoretical calculation predicted that hydrogen uptake depends strongly on the distances between corannulene molecules (inter-layer distance, ILD, and inter-molecular distance, IMD), in addition to temperature and gas pressure, as shown in Figure 8 .…”

“…Adsorption of hydrogen onto corannulene was theoretically studied by density functional theory (DFT) and molecular dynamic simulations, and also measured experimentally . Experimentally hydrogen uptake of 0.8 mass% was obtained at ambient temperature (298 K) under the hydrogen pressure of 72 bar, which agreed well with molecular dynamic calculation .…”

“…Hydrogen adsorption seems to be enhanced by the bowl‐shape of corannulene molecule and also by the induced dipole on the adsorbed hydrogen molecules due to the dipole moment of corannulene. Hydrogen uptake was expected to be significantly enhanced by Li‐doping of corannulene …”