Burkatzki M, Filippi C, Dolg M
Institute for Theoretical Chemistry, University of Cologne, Greinstrasse 4, 50939 Cologne, Germany.
J Chem Phys. 2007 Jun 21;126(23):234105. doi: 10.1063/1.2741534.
The authors present scalar-relativistic energy-consistent Hartree-Fock pseudopotentials for the main-group elements. The pseudopotentials do not exhibit a singularity at the nucleus and are therefore suitable for quantum Monte Carlo (QMC) calculations. They demonstrate their transferability through extensive benchmark calculations of atomic excitation spectra as well as molecular properties. In particular, they compute the vibrational frequencies and binding energies of 26 first- and second-row diatomic molecules using post-Hartree-Fock methods, finding excellent agreement with the corresponding all-electron values. They also show their pseudopotentials give superior accuracy than other existing pseudopotentials constructed specifically for QMC. Finally, valence basis sets of different sizes (VnZ with n=D,T,Q,5 for first and second rows, and n=D,T for third to fifth rows) optimized for our pseudopotentials are also presented.
作者提出了主族元素的标量相对论能量一致哈特里-福克赝势。这些赝势在原子核处不表现出奇异性，因此适用于量子蒙特卡罗（QMC）计算。他们通过对原子激发光谱以及分子性质进行广泛的基准计算来证明其可转移性。特别是，他们使用后哈特里-福克方法计算了26种第一和第二周期双原子分子的振动频率和结合能，发现与相应的全电子值有很好的一致性。他们还表明，他们的赝势比专门为QMC构建的其他现有赝势具有更高的精度。最后，还给出了针对我们的赝势优化的不同大小的价基组（第一和第二周期为n = D、T、Q、5的VnZ，第三至第五周期为n = D、T的VnZ）。
