臭氧同位素光谱中转动-振动耦合的作用
On the role of rotation-vibration coupling in the spectra of ozone isotopomers
摘要：
在超球坐标系下，考虑科里奥利耦合效应，建立了精确计算三原子分子振转耦合态的理论框架和计算机程序。简洁的最终公式推导出使用FBR和DVR方法与局部优化的基组和网格的有效组合的哈密顿矩阵的建设。首先，新的代码进行了测试，通过比较其结果与Kendrick的APH 3D程序。然后，精确计算的振转光谱进行了双取代对称（18 O 16 O 18 O）和不对称（18 O 18 O 16 O）臭氧同位素的总角动量高达J=5。再加上最近报道的单取代对称（16 O 18 O 16 O）和不对称（16 O 16 O 18 O）臭氧同位素异构体的类似数据，这些计算量化的科里奥利耦合效应的作用，在实验室实验和地球大气中观察到的大质量独立的同位素富集臭氧。结果表明，臭氧的Coriolis效应相对较小，这可以通过臭氧分子的转动常数与非对称顶转子行为的偏离、宇称分裂（Λ-加倍）的大小以及非对称与对称臭氧分子的振转配分函数的比值来证明。它的结论是，所有这些特性的同位素质量的影响，因为它们是由分子的整体对称性的影响。因此，科里奥利耦合效应不太可能是臭氧中氧同位素的非质量驱动分馏的原因。
英文摘要：
A theoretical framework and computer code are developed for accurate calculations of coupled rotational-vibrational states in triatomic molecules using hyper-spherical coordinates and taking into account the Coriolis coupling effect. Concise final formulae are derived for construction of the Hamiltonian matrix using an efficient combination of the FBR and DVR methods with locally optimized basis sets and grids. First, the new code is tested by comparing its results with those of the APH3D program of Kendrick. Then, accurate calculations of the ro-vibrational spectra are carried out for doubly substituted symmetric (18O16O18O) and asymmetric (18O18O16O) ozone isotopomers for total angular momentum up to J=5. Together with similar data recently reported for the singly substituted symmetric (16O18O16O) and asymmetric (16O16O18O) ozone isotopomers, these calculations quantify the role of the Coriolis coupling effect in the large mass-independent isotopic enrichment of ozone, observed in both laboratory experiments and the atmosphere of Earth. It is found that the Coriolis effect in ozone is relatively small, as evidenced by deviations of its rotational constants from the symmetric-top-rotor behavior, by the magnitudes of parity splittings (Λ-doubling), and by the ratios of ro-vibrational partition functions for asymmetric vs. symmetric ozone molecules. It is concluded that all of these characteristics are influenced by the isotopic masses as much as they are influenced by the overall symmetry of the molecule. It is therefore unlikely that the Coriolis coupling effect could be responsible for symmetry-driven mass-independent fractionation of oxygen isotopes in ozone.
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