Orthogonal Perturbations Resolve a Robust High-Frequency Relaxation in Nanocrystal-Derived Ag₄Zr₃S₈ Assemblies
- 1Loyola University Chicago
Abstract
Nanocrystal (NC)-derived ion-conducting solids combine compositionally tunable nanoscale building blocks with dense networks of particle–particle and electrode contacts, making it difficult to distinguish material-associated relaxation dynamics from assembly-dependent impedance. Here, colloidally synthesized Ag₄Zr₃S₈ NCs are consolidated into pellets and interrogated by pressure- and temperature-resolved electrochemical impedance spectroscopy using Ag + -blocking (Au) and Ag + non-blocking (Ag) contacts. An objective discontinuity criterion is used to identify a continuous high-frequency analysis window, which is evaluated by Bayesian Hilbert-transform diagnostics and distribution-of-relaxation-times (DRT) analysis. Across 0.43–8.67 MPa and 298–393 K, Au-contacted pellets exhibit a dominant sample-associated relaxation centered near tau ~ 10⁻⁶ s. The dominant mode remains within the microsecond relaxation-time regime across the investigated pressure and temperature ranges, while both its characteristic time and spectral weight vary non-monotonically with the applied perturbation. The same fast response persists after changing Au to Ag contacts and pellet preparation history, whereas slower DRT features are more configuration-sensitive. A frequency-matched dummy-cell control exhibits its principal relaxation approximately one decade later in time. These results demonstrate how orthogonal mechanical, thermal, electrode, and assembly perturbations can distinguish sample-associated relaxation dynamics from configuration-sensitive impedance in NC-derived chalcogenide solids.
Related
- Dielectric Relaxation and Equilibrium Thermodynamic Descriptors in Propanol Isomers: Radio-Frequency Measurements and openCOSMO-RS Analysis
- Supramolecular modulation of the mechanical properties of amino acid-functionalized cellulose nanocrystal films
- Tight binding of optically innocent bisphosphonate ligands to robust Tb3+-doped HfO2 nanocrystal surfaces
- Nanocraft: Nanocrystal Assembly and Functionalization Toolkit
- Synergistic Energetic Realignment and Interfacial Passivation via Perovskite Nanocrystal-Doped Spiro-OMeTAD for Efficient Planar Perovskite Solar Cells
BibTeX
@misc{xu2026orthogonal,
title = {{Orthogonal Perturbations Resolve a Robust High-Frequency Relaxation in Nanocrystal-Derived Ag₄Zr₃S₈ Assemblies}},
author = {Yunhao Xu and Isabella Campbell and Oluwaseyi Saliu and Simran Choudhary and Progna Banerjee},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv-2026-t7qrx/v2},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv-2026-t7qrx/v2},
note = {CC BY},
}
RIS
TY - UNPB
TI - Orthogonal Perturbations Resolve a Robust High-Frequency Relaxation in Nanocrystal-Derived Ag₄Zr₃S₈ Assemblies
AU - Yunhao Xu
AU - Isabella Campbell
AU - Oluwaseyi Saliu
AU - Simran Choudhary
AU - Progna Banerjee
PY - 2026
DA - 2026/10/08
PB - ChemRxiv
DO - 10.26434/chemrxiv-2026-t7qrx/v2
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv-2026-t7qrx/v2
AB - Nanocrystal (NC)-derived ion-conducting solids combine compositionally tunable nanoscale building blocks with dense networks of particle–particle and electrode contacts, making it difficult to distinguish material-associated relaxation dynamics from assembly-dependent impedance. Here, colloidally synthesized Ag₄Zr₃S₈ NCs are consolidated into pellets and interrogated by pressure- and temperature-resolved electrochemical impedance spectroscopy using Ag + -blocking (Au) and Ag + non-blocking (Ag) contacts. An objective discontinuity criterion is used to identify a continuous high-frequency analysis window, which is evaluated by Bayesian Hilbert-transform diagnostics and distribution-of-relaxation-times (DRT) analysis. Across 0.43–8.67 MPa and 298–393 K, Au-contacted pellets exhibit a dominant sample-associated relaxation centered near tau ~ 10⁻⁶ s. The dominant mode remains within the microsecond relaxation-time regime across the investigated pressure and temperature ranges, while both its characteristic time and spectral weight vary non-monotonically with the applied perturbation. The same fast response persists after changing Au to Ag contacts and pellet preparation history, whereas slower DRT features are more configuration-sensitive. A frequency-matched dummy-cell control exhibits its principal relaxation approximately one decade later in time. These results demonstrate how orthogonal mechanical, thermal, electrode, and assembly perturbations can distinguish sample-associated relaxation dynamics from configuration-sensitive impedance in NC-derived chalcogenide solids.
ER -