Zhang Y, Scanlon L G, Rottmayer M A, Balbuena P B
Department of Chemical Engineering, Texas A&M University, College Station, Texas 77843, USA.
J Phys Chem B. 2006 Nov 16;110(45):22532-41. doi: 10.1021/jp063963e.
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.
密度泛函理论和经典分子动力学模拟被用于研究锂掺杂的碗烯作为氢气吸附材料的前景。在B3LYP/6 - 311G(d,p)水平下的势能面扫描表明，与未掺杂的碗烯相比，分子氢与锂原子掺杂的碗烯配合物之间的相互作用增强。对4H₂-(Li₂-C₂₀H₁₀)进行MP2(FC)/6 - 31G(d,p)优化，得到H₂与Li相互作用的结合能为-1.48 kcal/mol，H₂与C相互作用的结合能为-0.92 kcal/mol，而使用MP2(full)/6 - 31G(d)分别报道的H₂在碗烯凹面和凸面物理吸附的结合能值为-0.94和-0.83 kcal/mol（《物理化学杂志B》2006年，110卷，7688 - 7694页）。经典分子动力学模拟预测，锂掺杂的碗烯组装体中的氢吸收量相对于未掺杂分子有显著增强，并且氢吸收能力取决于锂掺杂剂的浓度。对于Li₆-C₂₀H₁₀配合物，当吸附剂分子以6.5 Å的间距排列成堆叠构型时，在300 K和230 bar下氢吸收量为4.58 wt%，当层间距为10 Å时，在300 K和215 bar下氢吸收量达到6.5 wt%。
