Tunneling dynamics, symmetry, and far‐infrared spectrum of the rotating water trimer. I. Hamiltonian and qualitative model
Tunneling dynamics, symmetry, and far‐infrared spectrum of the rotating water trimer. I. Hamiltonian and qualitative model
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旋转水三聚体的隧道动力学、对称性和远红外光谱 I. 哈密顿量和定性模型。
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
P. Wormer
中科院分区：
文献类型：
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作者：
A. Avoird;E. Olthof;P. Wormer
哈密顿量是针对具有三个内部运动（单体绕其氢键的旋转）的旋转水三聚体而导出的。我们获得了动能算符的表达式，它是用于非旋转三聚体的早期启发式形式的重要扩展。首次给出了单轴单体角动量与整体三聚体旋转之间的科里奥利耦合算子。为了分析隧道效应和科里奥利分裂对三聚体能级的影响，我们引入了伪旋转和供体隧道效应的定性模型。通过扰动理论和置换反演群 G6 和 G48 的应用，我们分别获得了由于赝旋转和施主隧道效应引起的分裂的代数表达式。伪旋转不会产生任何内角动量，也不会产生一阶科里奥利分裂，但在二阶科里奥利耦合中会提升各种简并性并产生可观察到的......
A Hamiltonian is derived for the rotating water trimer with three internal motions—the rotations of the monomers about their hydrogen bonds. We obtain an expression of the kinetic energy operator, which is a non‐trivial extension of earlier heuristic forms used for the non‐rotating trimer. The Coriolis coupling operator between the single‐axis monomer angular momenta and the overall trimer rotation is given for the first time. To analyze the effects of the tunneling and Coriolis splittings on the energy levels of the trimer, we introduced a qualitative model for the pseudo‐rotation and donor tunneling. By perturbation theory and application of the permutation‐inversion groups G6 and G48 we obtain algebraic expressions for the splittings due to pseudo‐rotation and donor tunneling, respectively. The pseudo‐rotation does not produce any internal angular momentum and does not yield first order Coriolis splitting, but in second order the Coriolis coupling lifts various degeneracies and gives rise to observable...