Modeling of high-order terms in potential energy surface expansions using the reference-geometry Harris-Foulkes method.
Modeling of high-order terms in potential energy surface expansions using the reference-geometry Harris-Foulkes method.
复制标题
使用参考几何 Harris-Foulkes 方法对势能表面展开中的高阶项进行建模。
DOI：
10.1039/c3cp50172h
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发表时间：
2013
期刊：
影响因子：
--
通讯作者：
G. Rauhut
中科院分区：
文献类型：
--
作者：
P. Meier;G. Bellchambers;J. Klepp;F. Manby;G. Rauhut
参考几何Harris-Foulkes（RGHF）方法已被用来模拟高阶项的多维势能面（PES）的扩展内的精确的振动频率的计算超出谐波近似内所需的。该方法的关键步骤是在给定的参考结构处将电子密度定位到分子的原子，然后将这些原子中心的部分密度转移到扭曲结构的原子位置。这个概念已被用来评估3模式耦合项的多模式扩展的PES中产生的沃森哈密顿量。从振动组态相互作用（VCI）理论获得的振动频率的系统基准计算已经进行，以研究这种近似的基本模式的测试套件的28个分子的影响。
The reference-geometry Harris-Foulkes (RGHF) approach has been used to model high-order terms within the expansion of multi-dimensional potential energy surfaces (PES) as needed within the calculation of accurate vibrational frequencies beyond the harmonic approximation. The key step of this method is a localization of the electron density to the atoms of the molecule at a given reference structure and a subsequent transfer of these atom-centered partial densities to the atom positions of distorted structures. This concept has been used to evaluate the 3-mode coupling terms of a multi-mode expansion of the PES as arising in the Watson Hamiltonian. Systematic benchmark calculations for vibrational frequencies obtained from vibrational configuration interaction (VCI) theory have been performed in order to study the effects of this approximation on the fundamental modes of a test suite of 28 molecules.
关于超越谐波近似的振动谱的有效计算的选定方面
影响因子：
0.3
作者：
D. Oschetzki;M. Neff;P. Meier;F. Pfeiffer;G. Rauhut
通讯作者：
G. Rauhut