标题： 谐振振动频率计算中移动网格效应的研究 显示英文标题

标题： The Moving-Grid Effect in the Harmonic Vibrational Frequency Calculations with Numeric Atom-Centered Orbitals

摘要： 当使用原子中心积分网格时，属于某个原子的网格部分在该原子位移时也会移动。 在本文中，我们研究了在使用全电子全势数值原子中心轨道作为基组计算谐波振动频率时的移动网格效应。 我们发现，与一阶导数（即力）不同，移动网格效应对于二阶导数（即振动频率）起着关键作用。 进一步分析表明，主要影响的是对角线力常数项，这可以通过引入平移对称性来高效规避。 我们的方法已在有限系统（分子）和扩展系统（周期性）中得到验证。 显示英文摘要

摘要： When using atom-centered integration grids, the portion of the grid that belongs to a certain atom also moves when this atom is displaced. In the paper, we investigate the moving-grid effect in the calculation of the harmonic vibrational frequencies when using all-electron full-potential numeric atomic-centered orbitals as the basis set. We find that, unlike the first order derivative (i.e., forces), the moving-grid effect plays an essential role for the second order derivatives (i.e., vibrational frequencies). Further analysis reveals that predominantly diagonal force constant terms are affected, which can be bypassed efficiently by invoking translational symmetry. Our approaches have been demonstrated in both finite (molecules) and extended (periodic) systems.