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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Franck-condon fingerprinting of vibration-tunneling spectra
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Franck-condon fingerprinting of vibration-tunneling spectra

机译：振动隧道谱的弗兰克-康登指纹

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摘要

We introduce Franck-Condon fingerprinting as a method for assigning complex vibration-tunneling spectra. The B? state of thiophosgene (SCCl _2) serves as our prototype. Despite several attempts, assignment of its excitation spectrum has proved difficult because of near-degenerate vibrational frequencies, Fermi resonance between the C-Cl stretching mode and the Cl-C-Cl bending mode, and large tunneling splittings due to the out-of-plane umbrella mode. Hence, the spectrum has never been fitted to an effective Hamiltonian. Our assignment approach replaces precise frequency information with intensity information, eliminating the need for double resonance spectroscopy or combination differences, neither of which have yielded a full assignment thus far. The dispersed fluorescence spectrum of each unknown vibration-tunneling state images its character onto known vibrational progressions in the ground state. By using this Franck-Condon fingerprint, we were able to determine the predominant character of several vibration-tunneling states and assign them; in other cases, the fingerprinting revealed that the states are strongly mixed and cannot be characterized with a simple normal mode assignment. The assigned transitions from vibration-tunneling wave functions that were not too strongly mixed could be fitted within measurement uncertainty by an effective vibration-tunneling Hamiltonian. A fit of all observed vibration-tunneling states will require a full resonance-tunneling Hamiltonian.
机译：我们介绍了Franck-Condon指纹作为一种分配复杂的振动隧道光谱的方法。 B？状态的硫光气（SCCl _2）作为我们的原型。尽管进行了几次尝试，但由于几乎简并的振动频率，C-Cl拉伸模式和Cl-C-Cl弯曲模式之间的费米共振以及由于不存在的大的隧道裂隙，已证明难以分配其激发光谱。平面伞模式。因此，该频谱从未适合有效的哈密顿量。我们的分配方法用强度信息代替了精确的频率信息，从而消除了对双共振光谱或组合差的需求，到目前为止，这两种方法均未产生完整的分配。每个未知的振动隧道状态的分散荧光光谱将其特征成像到基态的已知振动进程中。通过使用Franck-Condon指纹，我们能够确定几个振动隧道状态的主要特征并对其进行分配。在其他情况下，指纹显示状态是强烈混合的，无法通过简单的正常模式分配来表征。通过有效的振动隧道哈密顿量，可以将分配给未太强烈混合的振动隧道波函数的跃迁拟合到测量不确定度内。对所有观察到的振动隧道状态的拟合将需要完整的共振隧道哈密顿量。

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