Off-the-shelf DFT-DISPersion methods: Are they now "on-trend" for organic molecular crystals?
Off-the-shelf DFT-DISPersion methods: Are they now "on-trend" for organic molecular crystals?
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DOI：
10.1063/1.5108829
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发表时间：
2019-07-28
影响因子：
4.4
通讯作者：
Roberts, Kevin J.
中科院分区：
文献类型：
--
作者：
Geatches, Dawn;Rosbottom, Ian;Roberts, Kevin J.
有机分子晶体包含长程色散相互作用，这对于密度泛函理论（DFT）等固态方法来说可能是一个挑战，并且在某些工业领域被忽视，而有利于经典方法来计算原子性质。因此，该出版物解决了有机晶体的色散校正DFT计算是否可以再现从实验中看到的结构和能量趋势的关键问题，即，现在的计算是否可以说是真正的趋势。在这项工作中，我们评估了三种最新的色散校正DFT方法在计算长程色散能方面的性能：D3（0）和D3（BJ）的成对方法和多体色散方法MBD@rsSCS。计算了羧酸和氨基酸两个同系有机分子晶体的能量学和优化结构。我们还使用了经典的力场方法（使用COMPASS II），并在可能的情况下将所有结果与实验数据进行比较。对于羧酸和氨基酸，晶格能的平均绝对误差分别为9.59和343.85 kJ/mol（COMPASS II）、10.17和16.23 kJ/mol（MBD@rsSCS）、10.57和18.76 kJ/mol [D3（0）]以及8.52和14.66 kJ/mol [D3（BJ）]。MBD@rsSCS产生的结构和能量趋势与实验趋势最接近，在两个系列中表现最一致，并与COMPASS II竞争。
Organic molecular crystals contain long-range dispersion interactions that can be challenging for solid-state methods such as density functional theory (DFT) to capture, and in some industrial sectors are overlooked in favor of classical methods to calculate atomistic properties. Hence, this publication addresses the critical question of whether dispersion corrected DFT calculations for organic crystals can reproduce the structural and energetic trends seen from experiment, i.e., whether the calculations can now be said to be truly on-trend. In this work, we assess the performance of three of the latest dispersion-corrected DFT methods, in calculating the long-range, dispersion energy: the pairwise methods of D3(0) and D3(BJ) and the many-body dispersion method, MBD@rsSCS. We calculate the energetics and optimized structures of two homologous series of organic molecular crystals, namely, carboxylic acids and amino acids. We also use a classical force field method (using COMPASS II) and compare all results to experimental data where possible. The mean absolute error in lattice energies is 9.59 and 343.85 kJ/mol (COMPASS II), 10.17 and 16.23 kJ/mol (MBD@rsSCS), 10.57 and 18.76 kJ/mol [D3(0)], and 8.52 and 14.66 kJ/mol [D3(BJ)] for the carboxylic acids and amino acids, respectively. MBD@rsSCS produces structural and energetic trends that most closely match experimental trends, performing the most consistently across the two series and competing favorably with COMPASS II.