H atom and heavy atom tunneling processes in tropolone
H atom and heavy atom tunneling processes in tropolone
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托酚酮中氢原子和重原子的隧道过程
DOI：
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发表时间：
2000
期刊：
影响因子：
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通讯作者：
R. L. Redington
中科院分区：
文献类型：
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作者：
R. L. Redington
用分子轨道方法计算了环庚三烯酚酮互变异构体之间的最小能量途径。这，与各种1D和2D削减的势能面（PES）的地形，揭示了{隧道骨架}/{隧道H原子}的互变异构化机制。在零点状态的H原子是本地化的O原子之一，直到环酚酮骨架成为足够的振动位移朝向C2 v配置，近相等的双最小势能函数（PEFs）出现的H原子振动。由此产生的两个O原子之间的H原子的离域允许骨架位移进行通过障碍和互变异构化过程完成。量子态N1中的v1（OH伸缩）能量强烈依赖于骨架几何形状，并且与缓慢的v22振动分离，它们对v22的显著不同的1D有效势能函数V22 eff [N1]做出贡献。V22 eff [N1=0]是一个n...
The minimum energy pathway leading between the tautomers of tropolone was calculated using molecular orbital (MO) methods. This, with various 1D and 2D cuts of the potential energy surface (PES) topography, reveals the {tunneling skeleton}/{tunneling H atom} mechanism for tautomerization. In the zero-point states the H atom is localized to one of the O atoms until the tropolone skeleton becomes sufficiently vibrationally displaced towards C2v configurations that near-equal double-minimum potential energy functions (PEFs) arise for the H atom vibration. The resulting delocalization of the H atom between the two O atom sites allows the skeletal displacement to proceed through the barrier and the tautomerization process to be completed. The v1 (OH stretching) energies in quantum states N1 are strongly dependent on the skeletal geometry and, adiabatically separated from the slow v22 vibration, they contribute to markedly different 1D effective potential energy functions V22eff[N1] for v22. V22eff[N1=0] is a n...