论文标题

在极端条件下的通用氢键对称动力学

Universal Hydrogen Bond Symmetrisation Dynamics Under Extreme Conditions

论文作者

Meier, Thomas, Trybel, Florian, Laniel, Dominique, Khandarkhaeva, Saiana, Ishii, Takayuki, Aslandukova, Alena, Dubrovinskaia, Natalia, Dubrovinsky, Leonid

论文摘要

尽管直接定位或探测氢子系统的挑战,但在极端条件下对氢键及其对称性的实验研究主要是由衍射方法驱动的。直到最近,就核量子效应,旋转跨界或直接结构跃迁而言,H键对称性已经解决。通常会导致矛盾的解释。在这里,我们提出了高分辨率\ textIt {intu} $^1 $ h-nmr在钻石砧细胞中的实验,研究了多种氢键系统的压力范围高达90 GPA,覆盖其各自的H键对称性。我们发现在NMR谐振线宽度的压力依赖性中,与氢迁移率的最大值,这是氢原子定位的前体相关的最小值。这些最小值独立于线性O-H-O单元的化学环境,可以在2.44至2.45Å之间的氧气氧气距离狭窄范围内找到,从而导致平均关键的临界氧气氧气距离$ \ bar {r} _ {rm oo} _ {\ rm oo}^{crit}^{crit}^{crit} = 2.4443 = 2.443(1)$Å(1)$Å(1)$Å。

The experimental study of hydrogen bonds and their symmetrisation under extreme conditions is predominantly driven by diffraction methods, despite challenges of localising or probing the hydrogen subsystems directly. Until recently, H-bond symmetrisation has been addressed in terms of either nuclear quantum effects, spin crossovers or direct structural transitions; often leading to contradictory interpretations when combined. Here, we present high-resolution \textit{in-situ} $^1$H-NMR experiments in diamond anvil cells investigating a wide range of hydrogen bonded systems at pressure ranges of up to 90 GPa covering their respective H-bond symmetrisation. We found pronounced minima in the pressure dependence of the NMR resonance line-widths associated with a maximum in hydrogen mobility, precursor to a localisation of hydrogen atoms. These minima, independent of of the chemical environment of the linear O -- H-O unit, can be found in a narrow range of oxygen-oxygen distances between 2.44 and 2.45 Å, leading to an average critical oxygen-oxygen distance of $\bar{r}_{\rm OO}^{crit}=2.443(1)$ Å.

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