Rarefied Basis Sets for the Calculation of Optical Tensors. 1. The Importance of Gradients on Hydrogen Atoms for the Raman Scattering Tensor
Rarefied Basis Sets for the Calculation of Optical Tensors. 1. The Importance of Gradients on Hydrogen Atoms for the Raman Scattering Tensor
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DOI：
10.1021/jp031284n
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发表时间：
2004-02
影响因子：
2.9
通讯作者：
Gérard Zuber;W. Hug
中科院分区：
文献类型：
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作者：
Gérard Zuber;W. Hug
对光学张量计算的基本要求进行了系统的研究。在两篇论文系列的第一篇中，我们对计算拉曼和拉曼旋光性 (ROA) 散射张量的各种基组的性能进行了比较。我们表明，如果振动问题在单独的计算中得到解决，则可以通过高度稀疏的集合获得与来自复杂集合的结果具有良好的定性和合理的定量一致性的结果。结果表明，对于含氢分子，稀薄基组有效性的基本要求是正确描述这些原子上电子张量的梯度，并且这只能通过在这些原子上包含适度扩散的 p 型函数来实现。此外，主原子氢和主原子氘伸缩振动的拉曼和 ROA 张量的正确渲染需要一层具有 va...
A systematic investigation has been undertaken on the basis set requirements for the calculation of optical tensors. In this first of a series of two papers we present a comparison of the performance of various basis sets for the calculation of the Raman and Raman optical activity (ROA) scattering tensor. We show that it is possible to obtain results in excellent qualitative and in reasonable quantitative agreement with those from complex sets by highly rarefied sets provided the vibrational problem is solved in a separate calculation. It is shown that, for hydrogen-containing molecules, a basic requirement for the effectiveness of rarefied basis sets is the proper description of gradients of electronic tensors on these atoms and that this can only be achieved by the inclusion of moderately diffuse p-type functions on these atoms. In addition, the correct rendering of the Raman and ROA tensor for main atom−hydrogen and main atom−deuterium stretching vibrations requires a layer of diffuse functions with va...