Multiresolution potential energy surfaces for vibrational state calculations
Multiresolution potential energy surfaces for vibrational state calculations
复制标题
用于振动状态计算的多分辨率势能面
DOI：
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发表时间：
2007
期刊：
影响因子：
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通讯作者：
K. Hirao
中科院分区：
文献类型：
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作者：
K. Yagi;S. Hirata;K. Hirao
针对多原子分子的非谐振动，提出了一种紧凑、鲁棒的多模势能面展开式（PES），其中单个多模项用各种不同的分辨率逼近，即电子结构方法、基集和功能形式。作为函数形式，我们探索了以下三种表示：网格上的数值、三次样条插值和泰勒展开。提出了一种有用的索引，可以快速识别保证高分辨率的重要多模项。对水和甲醛的应用表明，该方案可将PES计算效率提高11倍，且非谐波振动频率误差不大于~ 10cm−1。
A compact and robust many-mode expansion of potential energy surfaces (PES) is presented for anharmonic vibrations of polyatomic molecules, where the individual many-mode terms are approximated with various different resolutions, i.e., electronic structure methods, basis sets, and functional forms. As functional forms, the following three representations have been explored: numerical values on a grid, cubic spline interpolation, and a Taylor expansion. A useful index is proposed which rapidly identifies important many-mode terms that warrant a high resolution. Applications to water and formaldehyde demonstrate that the present scheme can increase the efficiency of the PES computation by a factor of up to 11 with the errors in anharmonic vibrational frequencies being no worse than ~ 10cm−1.