Vibrational Quantum Decoherence in Liquid Water,The Journal of Physical Chemistry Letters

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Vibrational Quantum Decoherence in Liquid Water
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2016-01-28 00:00:00 , DOI: 10.1021/acs.jpclett.5b02637
Tatsuya Joutsuka ₁ , Ward H. Thompson ₂ , Damien Laage ₁

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Traditional descriptions of vibrational energy transfer consider a quantum oscillator interacting with a classical environment. However, a major limitation of this simplified description is the neglect of quantum decoherence induced by the different interactions between two distinct quantum states and their environment, which can strongly affect the predicted energy-transfer rate and vibrational spectra. Here, we use quantum–classical molecular dynamics simulations to determine the vibrational quantum decoherence time for an OH stretch vibration in liquid heavy water. We show that coherence is lost on a sub-100 fs time scale due to the different responses of the first shell neighbors to the ground and excited OH vibrational states. This ultrafast decoherence induces a strong homogeneous contribution to the linear infrared spectrum and suggests that resonant vibrational energy transfer in H₂O may be more incoherent than previously thought.

中文翻译：

液态水中的振动量子退相干

振动能量转移的传统描述考虑了与经典环境相互作用的量子振荡器。但是，此简化描述的主要局限性是忽略了两个不同量子态及其环境之间不同相互作用所引起的量子退相干，这可能严重影响预测的能量传输速率和振动谱。在这里，我们使用量子经典分子动力学模拟来确定液态重水中OH拉伸振动的振动量子退相干时间。我们显示，由于第一个壳邻居对地面和激发的OH振动态的不同响应，在不到100 fs的时间尺度上失去了相干性。₂ O可能比以前认为的更加不连贯。

更新日期：2016-01-28

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