论文标题

使用超球坐标对科里奥利效应的理论处理,并应用于臭氧的RO振动光谱

Theoretical treatment of Coriolis effect using hyper-spherical coordinates, with application to the ro-vibrational spectrum of ozone

论文作者

Gayday, Igor, Teplukhin, Alexander, Kendrick, Brian K., Babikov, Dmitri

论文摘要

比较了几种用于描述旋转与振动之间相互作用的替代方法,并使用三局分子的超球坐标进行了对比。这些方法因选择z轴的选择和假设分子的转子形状而有所不同。对于每种情况,都会得出和分析旋转振动汉密尔顿基质的块结构,并明确说明每种方法的优点和缺点。然后,该理论被用来计算单一取代的臭氧的RO振动光谱。大致是16o18O16O和16O16O18O异构体的600个振动状态,旋转激发高达j = 5,并且两种反转平等(21600耦合RO振动状态总计)。计算和分析了不同平等状态(所谓的K双倍)之间的分裂。分别确定了不对称顶端转子项和科里奥利耦合项的作用,发现它们都影响了这些分裂,但在相反的方向上。因此,这两个效果部分取消了,残差分裂相对较小。 16o18O16O和16o16O18O在这项工作中报道的RO振动状态的能量与文献非常吻合(可用于低振动激发)。此处为高度激发的振动状态获得的新数据实现了臭氧对称和不对称同位素体中科里奥利效应的首次系统研究。

Several alternative methods for description of interaction between rotation and vibration are compared and contrasted using hyper-spherical coordinates for a triatomic molecule. These methods differ by the choice of z-axis and by the assumption of a prolate or oblate rotor shape of the molecule. For each case, block-structure of the rotational-vibrational Hamiltonian matrix is derived and analyzed, and the advantages and disadvantages of each method are made explicit. This theory is then employed to compute ro-vibrational spectra of singly substituted ozone; roughly, 600 vibrational states of 16O18O16O and 16O16O18O isomers combined, with rotational excitations up to J=5 and both inversion parities (21600 coupled ro-vibrational states total). Splittings between the states of different parities, so called K-doublings, are calculated and analyzed. The roles of the asymmetric-top rotor term and the Coriolis coupling term are determined individually, and it is found that they both affect these splittings, but in the opposite directions. Thus, the two effects partially cancel out, and the residual splittings are relatively small. Energies of the ro-vibrational states reported in this work for 16O18O16O and 16O16O18O are in excellent agreement with literature (available for low vibrational excitation). New data obtained here for the highly excited vibrational states enable the first systematic study of the Coriolis effect in symmetric and asymmetric isotopomers of ozone.

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