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Role of quantum fluctuations in structural dynamics of liquids of light molecules

机译:量子涨落在光液体结构动力学中的作用   分子

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摘要

A possible role of quantum effects, such as tunneling and zero-point energy,in the structural dynamics of supercooled liquids is studied by dielectricspectroscopy. Presented results demonstrate that the liquids, bulk3-methylpentane 3MP and confined normal and deuterated water have low glasstransition temperature and unusually low for their class of materials steepnessof the temperature dependence of structural relaxation, or fragility. Althoughwe do not find any signs of tunneling in structural relaxation of theseliquids, their unusually low fragility can be well described by the influenceof the quantum fluctuations. Confined water presents especially interestingcase in comparison to the earlier data on bulk low-density amorphous and vapordeposited water. Confined water exhibits much weaker isotope effect than bulkwater, although the effect is still significant. We show that it can beascribed to the change of the energy barrier for relaxation due to a decreasein the zero-point energy upon D-H substitution. The observed difference in thebehavior of confined and bulk water demonstrates high sensitivity of quantumeffects to the barrier heights and structure of water. Moreover, these resultsdemonstrate that extrapolation of confined water properties to the bulk waterbehavior is questionable.
机译:通过介电谱研究了量子效应(例如隧穿和零点能量)在过冷液体的结构动力学中的可能作用。目前的结果表明,液体,本体3-甲基戊烷3MP以及密闭的普通和重水具有较低的玻璃化转变温度,并且对于这类材料,其陡度与结构松弛或脆性的温度相关性异常低。尽管我们在这些液体的结构弛豫中没有发现任何隧穿迹象,但是它们的异常低的脆性可以通过量子涨落的影响得到很好的描述。与较早的有关大量低密度无定形和气相沉积水的数据相比,承压水特别有趣。尽管承压水仍然很显着,但其同位素作用要比散水弱得多。我们表明,这可以归因于由于D-H取代时零点能量的减少而导致的弛豫能垒的变化。观察到的承压水和散装水的行为差异表明,量子效应对水的势垒高度和结构高度敏感。而且,这些结果表明,将承压水特性外推到总体水行为上是有问题的。

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