中文摘要：

用第一性原理方法研究了H_2在（MgO）_9及（AlN）_（12）团簇上的吸附态、振动模式及熵.分析表明,吸附体系的振动中有六个简正模式可归为氢分子的振动;由于氢分子质量很小,零点能修正对吸附能有重要影响.利用振动配分函数计算了吸附氢分子的熵,表明吸附态H_2的熵主要决定于较低的同相振动的频率,并不完全与吸附强度相关;在标准大气压下70—350 K的温度范围内,吸附H_2的熵与气态H_2的熵之间存在很好的线性关系,吸附后H_2的熵减小约10.2R.

英文摘要：

The entropy and enthalpy changes upon absorption determine the equilibrium adsorption states, the adsorption/desorption kinetics, and the surface reaction rates. However, it is difficult to measure experimentally or calculate theoretically the entropy of adsorption state. Hydrogen is considered as the most promising candidate to solve the global energy problems, and the storage by adsorption on light porous solids constitutes a main avenue to research field. An ideal storage system should be able to operate under ambient conditions with high recycling capacity and suitable uptake-release kinetics. The entropy of adsorbed H2 molecules is of great significance for determining the optimum conditions for hydrogen storage and for designing the storage materials. To the best of our knowledge, however, the only report on the entropy of the adsorbed H2 molecules is that adsorbed on alkali-metal exchanged zeolites at temperatures around 100 K. Due to different assumptions of the entropy changes, the values of the optimum enthalpy ΔH reported in the publications cover a wide range. In this paper, the adsorption states, vibrational modes, and the entropies of H2 molecules adsorbed on （MgO）9 and （AlN）12 clusters are studied by using first principal method. The computation is performed by the second-order perturbation theory （MP2） with the triple zeta basis set including polarization functions 6-311G（d, p）. The very-tight convergence criterion is used to obtain reliable vibration frequencies. Analysis shows that six vibrational modes of the adsorption complexes can be attributed to the vibration of H2 molecule. For these normal modes, the amplitudes of the displacements of cluster atoms are usually two orders smaller than those of the hydrogen atoms. As the vibrational frequency is inversely proportional to the square root of the mass, the zero-point energy has an important influence on the adsorption energy. The ZPE correction exceeds half of the adsorption energy, and the adsorption on the anions is not sta