Benchmark coupled-cluster lattice energy of crystalline benzene and assessment of multi-level approximations in the many-body expansion
Benchmark coupled-cluster lattice energy of crystalline benzene and assessment of multi-level approximations in the many-body expansion
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DOI：
10.1063/5.0159410
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发表时间：
2023-06-21
影响因子：
4.4
通讯作者：
Sherrill, C. David
中科院分区：
文献类型：
--
作者：
Borca, Carlos H.;Glick, Zachary L.;Sherrill, C. David
多体展开法（MBE）是一种高效、并行计算有机晶体晶格能的方法。对于分子束外延产生的二聚体、三聚体和潜在的四聚体，在完全基组极限[CCSD（T）/CBS]下采用耦合簇单重、双重和微扰三重应该可以实现非常高的精度，但是这种蛮力方法对于除了最小分子之外的所有晶体似乎都是不切实际的。在这里，我们研究混合或多级方法，采用CCSD（T）/CBS仅用于最接近的二聚体和三聚体，并利用更快的方法，如Moller-Plesset微扰理论（MP2）更遥远的二聚体和三聚体。对于三聚体，MP2补充了三体分散的Axilrod-Teller-Muto（ATM）模型。MP2（+ATM）被证明是CCSD（T）/CBS的非常有效的替代品，除了最接近的二聚体和三聚体。使用CCSD（T）/CBS对四聚体的有限研究表明，四体贡献完全可以忽略。大量的CCSD（T）/CBS二聚体和三聚体数据在对分子晶体的近似方法进行基准测试时应该是有价值的，并且使我们能够看到，仅使用MP2对最接近的二聚体对晶格能的核心价贡献的文献估计是过度结合0.5 kJ mol（-1），在局部CCSD（T）中使用T0近似法估计的最接近的三聚体的三体贡献为0.7 kJ mol（-1）的欠结合。我们的CCSD（T）/CBS对0 K晶格能的最佳估计为-54.01 kJ mol（-1），而估计的实验值为-55.3 +/- 2.2 kJ mol（-1）。
The many-body expansion (MBE) is promising for the efficient, parallel computation of lattice energies in organic crystals. Very high accuracy should be achievable by employing coupled-cluster singles, doubles, and perturbative triples at the complete basis set limit [CCSD(T)/CBS] for the dimers, trimers, and potentially tetramers resulting from the MBE, but such a brute-force approach seems impractical for crystals of all but the smallest molecules. Here, we investigate hybrid or multi-level approaches that employ CCSD(T)/CBS only for the closest dimers and trimers and utilize much faster methods like Moller-Plesset perturbation theory (MP2) for more distant dimers and trimers. For trimers, MP2 is supplemented with the Axilrod-Teller-Muto (ATM) model of three-body dispersion. MP2(+ATM) is shown to be a very effective replacement for CCSD(T)/CBS for all but the closest dimers and trimers. A limited investigation of tetramers using CCSD(T)/CBS suggests that the four-body contribution is entirely negligible. The large set of CCSD(T)/CBS dimer and trimer data should be valuable in benchmarking approximate methods for molecular crystals and allows us to see that a literature estimate of the core-valence contribution of the closest dimers to the lattice energy using just MP2 was overbinding by 0.5 kJ mol(-1), and an estimate of the three-body contribution from the closest trimers using the T0 approximation in local CCSD(T) was underbinding by 0.7 kJ mol(-1). Our CCSD(T)/CBS best estimate of the 0 K lattice energy is -54.01 kJ mol(-1), compared to an estimated experimental value of -55.3 +/- 2.2 kJ mol(-1).