Institute of Applied Mechanics, National Taiwan University, Taipei 106, Taiwan, Republic of China.
J Chem Phys. 2010 Jan 14;132(2):024506. doi: 10.1063/1.3293129.
Intermolecular interaction potentials of the carbon tetrachloride dimer in 12 orientations have been calculated using the Hartree-Fock self-consistent theory and the second-order Moller-Plesset (MP2) perturbation theory. We have employed basis sets from Pople's medium size basis sets [up to 6-311++G(3df,3pd)] to Dunning's correlation consistent basis sets (up to aug-cc-pVQZ). The calculated MP2 potential data were employed to parametrize a four-site force field for molecular simulations. We performed molecular dynamics simulations using the ab initio force field and compared the simulation results to experiments. Quantitative agreements for the atomwise radial distribution functions, the self-diffusion coefficients, and the neutron and x-ray diffraction scattering functions over a wide range of experimental conditions can be obtained, thus validating the ab initio force field without using experimental data a priori.
采用 Hartree-Fock 自洽理论和二级 Møller-Plesset (MP2) 微扰理论计算了 12 个取向的四氯化碳二聚体的分子间相互作用势能。我们使用了从 Pople 的中等大小基组[最高到 6-311++G(3df,3pd)]到 Dunning 的相关一致基组(最高到 aug-cc-pVQZ)。计算的 MP2 势能数据被用来参数化分子模拟的四站点力场。我们使用从头算力场进行分子动力学模拟，并将模拟结果与实验进行比较。可以在广泛的实验条件下获得原子级径向分布函数、自扩散系数以及中子和 X 射线衍射散射函数的定量一致性，从而无需先验使用实验数据来验证从头算力场。
