Accurate Prediction of Lattice Energies and Structures of Molecular Crystals with Molecular Quantum Chemistry Methods
Accurate Prediction of Lattice Energies and Structures of Molecular Crystals with Molecular Quantum Chemistry Methods
复制标题
用分子量子化学方法准确预测分子晶体的晶格能量和结构
DOI：
10.1021/ct500833k
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发表时间：
2015
影响因子：
5.5
通讯作者：
Li Shuhua
中科院分区：
文献类型：
--
作者：
Fang Tao;Li Wei;Gu Fangwei;Li Shuhua
我们扩展的广义能量为基础的分裂（GEBF）的方法，分子晶体周期性边界条件（PBC）下，我们证明了各种分子晶体的方法的性能。通过这种方法，可以从一系列嵌入子系统的能量中获得分子晶体的晶格能，这些子系统可以用现有的先进分子量子化学方法计算。场补偿方法的使用允许该方法考虑无限晶体环境的远程静电相互作用，并使该方法几乎是不变性的。本方法的计算成本与单位晶胞中的分子数量成线性比例。示例性应用表明，具有显式相关量子化学方法的PBC-GEBF方法能够准确描述各种类型分子晶体的晶格能和结构。此外，这种方法可以用来量化各种分子间相互作用的理论晶格能的贡献。这种定性的认识对于合理设计分子晶体是非常有用的。
We extend the generalized energy-based fragmentation (GEBF) approach to molecular crystals under periodic boundary conditions (PBC), and we demonstrate the performance of the method for a variety of molecular crystals. With this approach, the lattice energy of a molecular crystal can be obtained from the energies of a series of embedded subsystems, which can be computed with existing advanced molecular quantum chemistry methods. The use of the field compensation method allows the method to take long-range electrostatic interaction of the infinite crystal environment into account and make the method almost translationally invariant. The computational cost of the present method scales linearly with the number of molecules in the unit cell. Illustrative applications demonstrate that the PBC-GEBF method with explicitly correlated quantum chemistry methods is capable of providing accurate descriptions on the lattice energies and structures for various types of molecular crystals. In addition, this approach can be employed to quantify the contributions of various intermolecular interactions to the theoretical lattice energy. Such qualitative understanding is very useful for rational design of molecular crystals.