TY - JOUR
T1 - The persistence of memory in ionic conduction probed by nonlinear optics
AU - Poletayev, Andrey D.
AU - Hoffmann, Matthias C.
AU - Dawson, James A.
AU - Teitelbaum, Samuel W.
AU - Trigo, Mariano
AU - Islam, M. Saiful
AU - Lindenberg, Aaron M.
N1 - Publisher Copyright:
© 2024, The Author(s).
PY - 2024/1/25
Y1 - 2024/1/25
N2 - Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries 1–3. For ionic conduction, the collective mechanisms 4,5, variation of conductivity with timescales 6–8 and confinement 9,10, and ambiguity in the phononic origin of translation 11,12, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.
AB - Predicting practical rates of transport in condensed phases enables the rational design of materials, devices and processes. This is especially critical to developing low-carbon energy technologies such as rechargeable batteries 1–3. For ionic conduction, the collective mechanisms 4,5, variation of conductivity with timescales 6–8 and confinement 9,10, and ambiguity in the phononic origin of translation 11,12, call for a direct probe of the fundamental steps of ionic diffusion: ion hops. However, such hops are rare-event large-amplitude translations, and are challenging to excite and detect. Here we use single-cycle terahertz pumps to impulsively trigger ionic hopping in battery solid electrolytes. This is visualized by an induced transient birefringence, enabling direct probing of anisotropy in ionic hopping on the picosecond timescale. The relaxation of the transient signal measures the decay of orientational memory, and the production of entropy in diffusion. We extend experimental results using in silico transient birefringence to identify vibrational attempt frequencies for ion hopping. Using nonlinear optical methods, we probe ion transport at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale, and demonstrate the connection between activated transport and the thermodynamics of information.
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U2 - 10.1038/s41586-023-06827-6
DO - 10.1038/s41586-023-06827-6
M3 - Article
C2 - 38267678
AN - SCOPUS:85183037270
SN - 0028-0836
VL - 625
SP - 691
EP - 696
JO - Nature
JF - Nature
IS - 7996
ER -