Implementation of the CCSD(T)-F12 method using cusp conditions.
Implementation of the CCSD(T)-F12 method using cusp conditions.
复制标题
使用尖点条件实施 CCSD(T)-F12 方法。
DOI：
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发表时间：
2008
期刊：
影响因子：
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通讯作者：
J. Noga
中科院分区：
文献类型：
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作者：
D. Bokhan;S. Ten;J. Noga
利用尖点条件实现了显关联耦合簇单簇和双簇微扰方法（CCSD（T）-F12）。对一组16个分子的数值测试表明，尖点条件和完全优化的CCSD（T）-F12方法之间的相关能在1 mE（h）内一致。用CCSD（T）-F_（12）方法对13个化学反应进行了基准计算，计算结果与实验值吻合，误差小于2kJ mol ~（-1）。它也表明，经常酉不变的anados不能完全满足单重态和三重态尖点条件在开壳层的情况下。我们提出了一个扩展的ANNERGY，它可以处理这两种情况。
The explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)-F12) is implemented using the cusp conditions. Numerical tests for a set of 16 molecules have shown agreement of correlation energies within 1 mE(h) between the cusp-condition and fully-optimized CCSD(T)-F12 methods. Benchmark calculations on 13 chemical reactions with the cusp-condition CCSD(T)-F12 method reproduce experimental enthalpies within 2 kJ mol(-1). It is also shown that regular unitary-invariant ansatz cannot exactly satisfy singlet and triplet cusp conditions in open-shell situations. We present an extended ansatz which can handle both conditions exactly.