Noncanonical Relationship between Heterogeneity and the Stokes-Einstein Breakdown in Deep Eutectic Solvents

被引：4

作者：

Srinivasan, H. ^{[1
,2
]}

Sharma, V. K. ^{[1
,2
]}

Sakai, V. Garcia ^{[3
]}

Mukhopadhyay, R. ^{[1
]}

Mitra, S. ^{[1
,2
]}

机构：

[1] Bhabha Atom Res Ctr, Solid State Phys Div, Mumbai 400085, India

[2] Homi Bhabha Natl Inst, Mumbai 400094, India

[3] Rutherford Appleton Lab, ISIS Neutron & Muon Source, Didcot OX11 0QX, England

来源：

JOURNAL OF PHYSICAL CHEMISTRY LETTERS | 2023年 / 14卷 / 43期

关键词：

ACETAMIDE; DIFFUSION; MECHANISM; DYNAMICS; WATER;

D O I：

10.1021/acs.jpclett.3c02132

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The relationship between Stokes-Einstein breakdown (SEB) and dynamical heterogeneity (DH) is of paramount importance in the physical chemistry of complex fluids. In this work, we employ neutron scattering to probe the DH and SEB in a series of deep eutectic solvents (DESs) composed of acetamide and lithium salts. Quasielastic neutron scattering experiments reveal SEB in the jump diffusion of acetamide, represented by a fractional Stokes-Einstein relationship. Among these DESs, lithium perchlorate exhibits the most pronounced SEB while lithium bromide displays the weakest. Concurrently, elastic incoherent neutron scans identify that bromide DES is the most heterogeneous and perchlorate is the least. For the first time, our study unveils a counterintuitive incommensurate relationship between DH and SEB. Further, it reveals the intricate contrasting nature of the SEB-DH relationship when investigated in proximity to the glass-transition temperature and further away from it.

引用

页码：9766 / 9773

页数：8

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