ON THE MULTIDIMENSIONALITY OF INTRAMOLECULAR HYDROGEN BOND DYNAMICS: HYDROGEN TRANSFER AND IVR IN 3,7-DICHLOROTROPOLONE
ON THE MULTIDIMENSIONALITY OF INTRAMOLECULAR HYDROGEN BOND DYNAMICS: HYDROGEN TRANSFER AND IVR IN 3,7-DICHLOROTROPOLONE
复制标题
分子内氢键动力学的多维性：3,7-二氯托普酮中的氢转移和 IVR
DOI：
10.1142/s0219633604001264
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发表时间：
2004
影响因子：
2.4
通讯作者：
O. Kühn
中科院分区：
文献类型：
--
作者：
K. Giese;D. Lahav;O. Kühn
在这项工作中，我们研究了托酚酮衍生物（即 3,7-二氯托酚酮）中与氢转移相关的分子内振动能量重新分布。我们的量子模拟基于笛卡尔反应面哈密顿量以及用于波包传播的多配置时间相关 Hartree 方法。我们比较了分别具有 6 维和 14 维的两个模型系统的结果。 6D 模型考虑了最强的耦合模式，而 14D 模型则包括耦合明显较弱的其他模式。两种模型的线性吸收光谱都显示了 OH 伸缩带的发展。此外，结果表明，尽管 14D 系统中的附加模式耦合明显较弱，但 OH 伸缩激发的衰减行为存在质的差异。还讨论了当前反应表面方法的局限性。
In this work, we investigate the intramolecular vibrational energy redistribution associated with the hydrogen transfer in a derivative of tropolone, namely 3,7-dichlorotropolone. Our quantum simulation is based on the Cartesian reaction surface Hamiltonian together with the multi-configurational time-dependent Hartree approach for the wave-packet propagation. We compare results for two model systems with 6 and 14 dimensions, respectively. The 6D model accounts for the most strongly coupled modes, whereas the 14D model includes further modes with significantly weaker couplings. The linear absorption spectrum of both models shows the development of an OH-stretching band. Furthermore the results show that despite the fact, that the additional modes in the 14D system couple significantly weaker, there are qualitative differences in the decay behavior of an OH-stretching excitation. Limitations of the present reaction surface approach are also discussed.