Method of increments for the halogen molecular crystals: Cl, Br, and I.
Method of increments for the halogen molecular crystals: Cl, Br, and I.
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DOI：
10.1063/1.4896230
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发表时间：
2014-09
期刊：
影响因子：
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通讯作者：
K. Steenbergen;N. Gaston;Carsten Müller;B. Paulus
中科院分区：
文献类型：
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作者：
K. Steenbergen;N. Gaston;Carsten Müller;B. Paulus
增量法（MI）计算揭示了固体氯，溴，碘结合的n体相关贡献。二级结合贡献以及d-相关能量估计和比较每个固体卤素。我们说明，结合完全是由两体相关效应，占总相关能的80%以上。单体、三体和交换贡献都是排斥的。使用密度拟合（DF）本地耦合集群单打，双打，和微扰三重增量计算，我们得到了很好的协议与实验的内聚能。从DF局部二阶Møller-Plesset微扰（LMP 2）的MI结果产生相当大的超限内聚能。密度泛函理论和周期LMP 2方法的比较计算也被证明是不太准确的固体卤素。
Method of increments (MI) calculations reveal the n-body correlation contributions to binding in solid chlorine, bromine, and iodine. Secondary binding contributions as well as d-correlation energies are estimated and compared between each solid halogen. We illustrate that binding is entirely determined by two-body correlation effects, which account for >80% of the total correlation energy. One-body, three-body, and exchange contributions are repulsive. Using density-fitting (DF) local coupled-cluster singles, doubles, and perturbative triples for incremental calculations, we obtain excellent agreement with the experimental cohesive energies. MI results from DF local second-order Møller-Plesset perturbation (LMP2) yield considerably over-bound cohesive energies. Comparative calculations with density functional theory and periodic LMP2 method are also shown to be less accurate for the solid halogens.