Centre for Quantum Materials and Technology, School of Mathematics and Physics, Queen's University Belfast, Belfast BT7 1NN, Northern Ireland, United Kingdom.
J Phys Chem Lett. 2023 Feb 16;14(6):1542-1547. doi: 10.1021/acs.jpclett.2c03896. Epub 2023 Feb 6.
Recent work has shown that the dynamics of hydrogen bonds in pure clays are affected by nuclear quantum fluctuations, with different effects for the hydrogen bonds holding different layers of the clay together and for those within the same layer. At the clay-water interface there is an even wider range of types of hydrogen bond, suggesting that the quantum effects may be yet more varied. We apply classical and thermostated ring polymer molecular dynamics simulations to show that nuclear quantum effects accelerate hydrogen-bond dynamics to varying degrees. By interpreting the results in terms of the extended jump model of hydrogen-bond switching, we can understand the origins of these effects in terms of changes in the quantum kinetic energy of hydrogen atoms during an exchange. We also show that the extended jump mechanism is applicable not only to the hydrogen bonds involving water, but also those internal to the clay.
最近的研究表明，氢键的动力学在纯粘土中受到核量子涨落的影响，对于将不同层的粘土结合在一起的氢键和同一层内的氢键有不同的影响。在粘土-水界面上存在更广泛类型的氢键，这表明量子效应可能更加多样化。我们应用经典和恒温环聚合物分子动力学模拟表明，核量子效应在不同程度上加速了氢键的动力学。通过用氢键交换的扩展跳跃模型来解释结果，我们可以根据氢原子在交换过程中量子动能的变化来理解这些效应的起源。我们还表明，扩展跳跃机制不仅适用于涉及水的氢键，也适用于粘土内部的氢键。
