• 主题
高级搜索  >
历史搜索 清空历史
首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Algebraic-Matrix Calculation of Vibrational Levels of Triatomic Molecules
【24h】

Algebraic-Matrix Calculation of Vibrational Levels of Triatomic Molecules

机译：三原子分子振动能级的代数矩阵计算

获取原文
获取原文并翻译 | 示例
           
页面导航
  • 摘要
  • 著录项
  • 相似文献
  • 相关主题

摘要

We introduce an accurate and efficient algebraic technique for the computation of the vibrational spectra of triatomic molecules, of both linear and bent equilibrium geometry. The full three-dimensional potential energy surface (PES), which can be based on entirely ab initio data, is parametrized as a product Morse-cosine expansion, expressed in bond angle internal coordinates, and includes explicit interactions among the local modes. We describe the stretching degrees of freedom in the framework of a Morse-type expansion on a suitable algebraic basis, which provides exact analytical expressions for the elements of a sparse Hamiltonian matrix. Likewise, we use a cosine power expansion on a spherical harmonics basis for the bending degree of freedom. The resulting matrix representation in the product space is very sparse, and vibrational levels and eigenfunctions can be obtained by efficient diagonalization techniques. We apply this method to carbonyl sulfide, hydrogen cyanide, water, and nitrogen dioxide. When we base our calculations on high-quality PESs tuned to the experimental data, the computed spectra are in very good agreement with the observed band origins.
机译：我们介绍了一种精确高效的代数技术，用于计算线性和弯曲平衡几何结构的三原子分子的振动谱。可以完全基于从头算数据的完整三维势能面（PES）参数化为产品莫尔斯-余弦展开，以键角内部坐标表示，并且包括局部模式之间的显式相互作用。我们在适当的代数基础上描述了Morse型展开框架中的拉伸自由度，它为稀疏哈密顿矩阵的元素提供了精确的解析表达式。同样，我们使用基于球谐函数的余弦功率展开来表示弯曲的自由度。乘积空间中所得的矩阵表示非常稀疏，并且可以通过有效的对角化技术获得振动水平和本征函数。我们将此方法应用于羰基硫，氰化氢，水和二氧化氮。当我们根据调谐到实验数据的高质量PES进行计算时，计算出的光谱与观察到的谱带起源非常吻合。

著录项

相似文献

  • 外文文献
  • 中文文献
  • 专利
获取原文

客服邮箱：kefu@zhangqiaokeyan.com

京公网安备：11010802029741号 ICP备案号：京ICP备15016152号-6 六维联合信息科技 (北京) 有限公司©版权所有

  • 客服微信

  • 服务号