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Main Authors: Ying, Penghua, Liang, Ting, Chen, Yun, Chen, Yan, Xiong, Shiyun, Fan, Zheyong, Xu, Jianbin, Liu, Yilun
Format: Preprint
Published: 2026
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Online Access:https://arxiv.org/abs/2604.03783
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author Ying, Penghua
Liang, Ting
Chen, Yun
Chen, Yan
Xiong, Shiyun
Fan, Zheyong
Xu, Jianbin
Liu, Yilun
author_facet Ying, Penghua
Liang, Ting
Chen, Yun
Chen, Yan
Xiong, Shiyun
Fan, Zheyong
Xu, Jianbin
Liu, Yilun
contents While crystalline materials with glass-like thermal conductivity are fundamentally intriguing, structurally triggering the transition from propagating to diffusive heat transport within a single framework remains a formidable challenge. Here, using extensive machine learning molecular dynamics, we demonstrate a fundamental thermal transport crossover in metal-organic frameworks. We reveal that grafting flexible side chains onto a pristine MOF backbone acts as a structural switch, strongly reducing the thermal conductivity by $\sim$70% (from $\sim 0.7$ to $\sim 0.2\ \text{W m}^{-1}\text{K}^{-1}$ at 300 K). Crucially, the functionalized derivatives exhibit a drastic transition from a classical Peierls $\sim 1/T$ decay to an anomalous, temperature-independent glass-like plateau. Reciprocal- and real-space analyses reveal the microscopic origins: the side chains act as built-in local resonators that trap acoustic energy via strong low-frequency resonant hybridization, while simultaneously inducing extreme steric crowding. Consequently, the heat-carrying phonon modes become critically damped, with their mean free paths strictly confined to the nanometer scale and their lifetimes collapsing to the Ioffe-Regel limit. This work establishes a highly programmable molecular engineering strategy to dismantle the phonon gas model, forcing crystalline frameworks into an extreme diffusive transport regime.
format Preprint
id arxiv_https___arxiv_org_abs_2604_03783
institution arXiv
publishDate 2026
record_format arxiv
spellingShingle Structurally Triggered Breakdown of the Phonon Gas Model in Crystalline Metal-Organic Frameworks
Ying, Penghua
Liang, Ting
Chen, Yun
Chen, Yan
Xiong, Shiyun
Fan, Zheyong
Xu, Jianbin
Liu, Yilun
Soft Condensed Matter
Computational Physics
While crystalline materials with glass-like thermal conductivity are fundamentally intriguing, structurally triggering the transition from propagating to diffusive heat transport within a single framework remains a formidable challenge. Here, using extensive machine learning molecular dynamics, we demonstrate a fundamental thermal transport crossover in metal-organic frameworks. We reveal that grafting flexible side chains onto a pristine MOF backbone acts as a structural switch, strongly reducing the thermal conductivity by $\sim$70% (from $\sim 0.7$ to $\sim 0.2\ \text{W m}^{-1}\text{K}^{-1}$ at 300 K). Crucially, the functionalized derivatives exhibit a drastic transition from a classical Peierls $\sim 1/T$ decay to an anomalous, temperature-independent glass-like plateau. Reciprocal- and real-space analyses reveal the microscopic origins: the side chains act as built-in local resonators that trap acoustic energy via strong low-frequency resonant hybridization, while simultaneously inducing extreme steric crowding. Consequently, the heat-carrying phonon modes become critically damped, with their mean free paths strictly confined to the nanometer scale and their lifetimes collapsing to the Ioffe-Regel limit. This work establishes a highly programmable molecular engineering strategy to dismantle the phonon gas model, forcing crystalline frameworks into an extreme diffusive transport regime.
title Structurally Triggered Breakdown of the Phonon Gas Model in Crystalline Metal-Organic Frameworks
topic Soft Condensed Matter
Computational Physics
url https://arxiv.org/abs/2604.03783