基组对CHCl_3超极化率的影响：高斯型轨道、数值基组和实空间网格
Basis set effects on the hyperpolarizability of CHCl_3: Gaussian-type orbitals, numerical basis sets and real-space grids
摘要：
超极化率的计算通常比线性极化率更难收敛于基组大小。为了理解这些收敛问题并获得准确的从头算值，我们比较了使用三种不同基组（高斯型轨道、数值基组和实空间网格）计算气相氯仿分子（CHCl_3）的静态超极化率。虽然所有这些方法都可以产生类似的结果，但需要惊人的大，分散的基组才能实现收敛到可比值。这些结果解释的局部极化率和超极化率密度。我们发现，超极化率是非常敏感的分子结构，我们也评估的振动贡献和频率色散的意义。
英文摘要：
Calculations of the hyperpolarizability are typically much more difficult to converge with basis set size than the linear polarizability. In order to understand these convergence issues and hence obtain accurate ab initio values, we compare calculations of the static hyperpolarizability of the gas-phase chloroform molecule (CHCl_3) using three different kinds of basis sets: Gaussian-type orbitals, numerical basis sets, and real-space grids. Although all of these methods can yield similar results, surprisingly large, diffuse basis sets are needed to achieve convergence to comparable values. These results are interpreted in terms of local polarizability and hyperpolarizability densities. We find that the hyperpolarizability is very sensitive to the molecular structure, and we also assess the significance of vibrational contributions and frequency dispersion.
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