Dinpajooh Mohammadhasan, Biasin Elisa, Nienhuis Emily T, Mergelsberg Sebastian T, Benmore Chris J, Schenter Gregory K, Fulton John L, Kathmann Shawn M, Mundy Christopher J
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, USA.
Advanced Photon Source, Argonne National Laboratory, Chicago, Illinois 60439, USA.
J Chem Phys. 2024 Oct 21;161(15). doi: 10.1063/5.0234518.
We establish the connection between the measured small angle x-ray scattering signal and the charge-charge correlations underlying Kirkwood transitions (KTs) in 1:1, 2:1, and 3:1 aqueous electrolytes. These measurements allow us to obtain underscreening lengths for bulk electrolytes independently verified by theory and simulations. Furthermore, we generalize the concept of KTs beyond those theoretically predicted for 1:1 electrolytes, which involves the inverse screening length, a0, and the inverse periodicity length, Q0. Above the KTs, we find a universal scaling of a0∝c-ζ/3 and Q0 ∝ c1/3 for the studied electrolyte solutions, where ζ is the ionic strength factor.
我们建立了测量的小角X射线散射信号与1:1、2:1和3:1水性电解质中柯克伍德转变（KTs）背后的电荷-电荷相关性之间的联系。这些测量使我们能够获得本体电解质的欠屏蔽长度，该长度已通过理论和模拟独立验证。此外，我们将KTs的概念推广到超出理论上预测的1:1电解质的范围，这涉及到反屏蔽长度a0和反周期性长度Q0。在KTs之上，我们发现对于所研究的电解质溶液，a0∝c-ζ/3和Q0 ∝ c1/3具有通用标度，其中ζ是离子强度因子。
