Kumar Shubham, Bagchi Biman
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore 560012, India.
J Chem Phys. 2022 Jun 14;156(22):224501. doi: 10.1063/5.0090811.
We report the existence of disparate static and dynamic correlation lengths that could describe the influence of confinement on nanoconfined water (NCW). Various aspects of viscous properties, such as anisotropy and viscoelasticity, of NCW are studied by varying the separation distance "d" between two confining hydrophobic plates. The transverse component of the mean square stress exhibits slow spatial decay (measured from the surface) beyond ∼1.8 nm, which was not reported before. The static correlation length obtained from fitting the exponential decay of the transverse mean-square stress with d is 0.75 nm, while the decay time of the stress-stress time correlation function gives a dynamic correlation length of only 0.35 nm. The shortness of the dynamic correlation length seems to arise from the low sensitivity of orientational relaxation to confinement. In the frequency-dependent viscosity, we observe a new peak at about 50 cm that is not present in the bulk. This new peak is prominent even at 3 nm separations. The peak is absent in the bulk, although it is close to the intermolecular -O-O-O- bending mode well known in liquid water. We further explore the relationship between diffusion and viscosity in NCW by varying d.
我们报告了不同的静态和动态关联长度的存在,它们可以描述限制对纳米限域水(NCW)的影响。通过改变两个限制疏水板之间的分离距离“d”,研究了NCW粘性特性的各个方面,如各向异性和粘弹性。均方应力的横向分量在超过约1.8纳米(从表面测量)处表现出缓慢的空间衰减,这是之前未报道过的。通过将横向均方应力的指数衰减与d拟合得到的静态关联长度为0.75纳米,而应力-应力时间关联函数的衰减时间给出的动态关联长度仅为0.35纳米。动态关联长度较短似乎源于取向弛豫对限制的低敏感性。在频率依赖的粘度中,我们在约50厘米处观察到一个在本体中不存在的新峰。即使在3纳米的分离距离下,这个新峰也很明显。该峰在本体中不存在,尽管它接近液态水中众所周知的分子间-O-O-O-弯曲模式。我们通过改变d进一步探索了NCW中扩散与粘度之间的关系。