论文标题

纠正配置相互作用电子结构计算中的残余误差

Correction of Residual Errors in Configuration Interaction Electronic Structure Calculations

论文作者

Whitten, Jerry L.

论文摘要

根据可以将能量缺陷映射到原子区域的假设,讨论了纠正分子和其他电子系统构型相互作用(CI)计算的剩余能量误差的方法。这些方法不考虑激发的详细性质,而是定义每个电子在特定原子所独有的电子的缺陷能量。缺陷能量贡献是根据对双原子和氢化物分子的计算确定的,然后应用于其他系统。将计算的能量与实验性热力学和光谱数据进行了比较,该数据主要代表了各种键合环境,主要是41个有机分子。最严格的测试是基于严重截断的虚拟空间,在该空间中,删除了较高的球形谐波函数。初始CI计算的误差很大,但是在每种情况下,包括缺陷校正都会使计算出的CI能量与实验值一致。该方法还应用于采用更大基集且无截断的虚拟空间的耦合群集计算的NIST汇编。校正与总能量与实验值非常吻合时表现出极好的一致性。该方法的扩展应用于SC,Ti,V,Mn,Cr,Fe,Fe,Co,Ni和Cu的DMSN状态,显着改善了与光谱值的计算过渡能的一致性。

Methods for correcting residual energy errors of configuration interaction (CI) calculations of molecules and other electronic systems are discussed based on the assumption that the energy defect can be mapped onto atomic regions. The methods do not consider the detailed nature of excitations, but instead define a defect energy per electron that that is unique to a specific atom. Defect energy contributions are determined from calculations on diatomic and hydride molecules and then applied to other systems. Calculated energies are compared with experimental thermodynamic and spectroscopic data for a set of forty-one mainly organic molecules representing a wide range of bonding environments. The most stringent test is based on a severely truncated virtual space in which higher spherical harmonic basis functions are removed. The errors of the initial CI calculations are large, but in each case, including defect corrections brings calculated CI energies into agreement with experimental values. The method is also applied to a NIST compilation of coupled-cluster calculations that employ a larger basis set and no truncation of the virtual space. The corrections show excellent consistency with total energies in very good agreement with experimental values. An extension of the method is applied to dmsn states of Sc, Ti, V, Mn, Cr, Fe, Co, Ni and Cu, significantly improving the agreement of calculated transition energies with spectroscopic values.

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