相互作用能和相互作用诱导性质显式关联计算中的尺寸一致性和平衡修正
Size consistency and counterpoise correction in explicitly correlated calculations of interaction energies and interaction-induced properties
摘要：
显式相关计算的相互作用能与波函数，包括所有粒子间的距离已经遭受到目前为止，从缺乏大小一致性造成的困难，以确定相应的应用二聚体的基础上的单体能量。因此，不可能获得在无限单体间距离$R$处消失的相互作用能。这大大降低了在二聚体能量误差与相互作用能本身相当的距离处计算的准确性。同样的问题也发生在计算相互作用引起的性质。在这次交流中，我们将展示如何绕过这一困难，并获得相互作用能或相互作用引起的性能，消失在大$R$。这是通过放松泡利原理在对角化的非相互作用单体的哈密顿量。用于这种对角化的基函数属于由适合于单体自旋状态的表示的乘积诱导的二聚体的置换群的表示。基组的非线性参数仅针对Hilbert空间的Pauli允许扇区中的二聚体进行优化。以这种方式，获得非相互作用单体的$R$依赖性能量，并且相应的相互作用能量包括基组叠加误差的平衡校正。该程序的效率证明了两个氢原子的相互作用，其中准确的参考数据是已知的。
英文摘要：
Explicitly correlated calculations of interaction energies with wave functions that include all interparticle distances have suffered so far from the lack of size-consistency resulting from the difficulty to define monomer energies corresponding to the applied dimer basis. As a consequence it has not been possible to obtain interaction energies vanishing at infinite intermonomer distance $R$. This has dramatically reduced the accuracy of calculations at distances where the error in the dimer energy was comparable with the interaction energy itself. The same problem occurs in calculations of interaction-induced properties. In this communication we show how to circumvent this difficulty and obtain interaction energies or interaction-induced properties that vanish at large $R$. This is achieved by relaxing the Pauli principle in the diagonalization of the Hamiltonian of noninteracting monomers. The basis functions used for this diagonalization belong to the representation of the permutation group of the dimer induced by the product of representations appropriate for the monomer spin states. Nonlinear parameters of the basis set are optimized only for the dimer in the Pauli-allowed sector of the Hilbert space. In this way, one obtains $R$-dependent energy of noninteracting monomers and the corresponding interaction energy includes a counterpoise correction for the basis set superposition error. The efficiency of this procedure is demonstrated for the interaction of two hydrogen atoms where accurate reference data are known.
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