The role of axis embedding on rigid rotor decomposition analysis of variational rovibrational wave functions.
The role of axis embedding on rigid rotor decomposition analysis of variational rovibrational wave functions.
复制标题
轴嵌入对变分振动波函数刚性转子分解分析的作用。
DOI：
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发表时间：
2012
影响因子：
4.4
通讯作者：
A. Császár
中科院分区：
文献类型：
--
作者：
Tamás Szidarovszky;C. Fábri;A. Császár
通过刚性转子分解（RRD）协议的近似旋转表征的变分振转波函数的哈密顿量的基础上任意设置的内部坐标和轴嵌入。一个有效的和一般的程序，允许采用Eckart嵌入任意多原子哈密顿通过一个完全数值的方法。RRD表形成的投影旋转振动波函数到产品的刚性转子基函数和先前确定的振动本征态产生刚性转子标签的振转本征态通过选择最大的重叠。嵌入相关的RRD分析进行，高能量和旋转激发，为H（2）（16）O同位素的水分子。无论选择的嵌入，RRD程序证明是有效的，在低能量和J值提供明确的旋转分配。H（2）（16）O的振转态的旋转标记被证明在超过约10，000 cm（-1）时越来越困难，接近水分子线性的障碍。对于中等能量和激发的Eckart嵌入产生最大的RRD系数，从而提供最大数量的明确的旋转标签。
Approximate rotational characterization of variational rovibrational wave functions via the rigid rotor decomposition (RRD) protocol is developed for Hamiltonians based on arbitrary sets of internal coordinates and axis embeddings. An efficient and general procedure is given that allows employing the Eckart embedding with arbitrary polyatomic Hamiltonians through a fully numerical approach. RRD tables formed by projecting rotational-vibrational wave functions into products of rigid-rotor basis functions and previously determined vibrational eigenstates yield rigid-rotor labels for rovibrational eigenstates by selecting the largest overlap. Embedding-dependent RRD analyses are performed, up to high energies and rotational excitations, for the H(2) (16)O isotopologue of the water molecule. Irrespective of the embedding chosen, the RRD procedure proves effective in providing unambiguous rotational assignments at low energies and J values. Rotational labeling of rovibrational states of H(2) (16)O proves to be increasingly difficult beyond about 10,000 cm(-1), close to the barrier to linearity of the water molecule. For medium energies and excitations the Eckart embedding yields the largest RRD coefficients, thus providing the largest number of unambiguous rotational labels.
DOI：
10.1016/j.jqsrt.2010.02.009
发表时间：
2010-06-01
影响因子：
2.3
作者：
Csaszar, Attila G.;Matyus, Edit;Tennyson, Jonathan
通讯作者：
Tennyson, Jonathan