Physics-Constrained Learning of Dose-Dependent Spectral Degradation in Metal--Organic Frameworks from In Situ Low-Loss EELS

TL;DR

This study employs a physics-informed neural network to model dose-dependent spectral degradation in metal-organic frameworks using in situ low-loss EELS, revealing key insights into material stability and spectral changes.

Contribution

It introduces a novel PINN-based framework that quantitatively links in situ spectroscopy to beam-induced degradation in MOFs, incorporating spectral descriptors and degradation equations.

Findings

C--O and C--C linkers are most dose-sensitive.

Half-integrity thresholds are around 1000 e$^-$/ ext{ A}$^2$.

Low-energy $ ext{ extpi}$--$ ext{ extpi}^*$ response involves oscillator-strength redistribution.

Abstract

Electron-beam irradiation limits atomic-resolution characterization of beam-sensitive hybrid materials, yet quantitative models that connect \textit{in situ} spectroscopy to dose-dependent degradation remain scarce. Here we use a physics-informed neural network (PINN) to model beam-induced spectral evolution in MIL-101(Fe) from an in situ low-loss electron energy-loss spectroscopy (EELS) dose series. Each spectrum is reduced to fixed-window low-loss descriptors, $\tilde n_{\mathrm{eff},j}(\Phi)=\int_{\mathcal{W}_j}S(E,\Phi)\,dE$, evaluated over nominal $\pi$--$\pi^{*}$, C--C, C--O, and M--O windows. These descriptors are relative window-integrated low-loss spectral areas, not absolute f-sum-rule effective electron numbers. For each spectral channel, a latent integrity variable $C_i(\Phi)$ obeys the same uncoupled power-law degradation equation in normalized dose space, $dC_i/d\phi=-k_i C_i^{p_i}$, regularized by monotonicity, boundedness, and a single hierarchy prior $k_{\mathrm{C\text{-}O}}\geq k_{\mathrm{C\text{-}C}}$. Applied to nine dose frames spanning 152--1368~e$^-$/\AA$^2$, the ensemble PINN identifies C--O and C--C as the most strongly dose-sensitive linker-associated channels, with half-integrity thresholds of approximately $1.0\times10^3$~e$^-$/\AA$^2$. The 1--3~eV $\pi$--$\pi^{*}$-labelled window increases with dose and is therefore interpreted as a mixed low-energy response, likely involving oscillator-strength redistribution rather than direct monotonic loss of a single bond population. The framework provides a dose-dependent, spectroscopy constrained description of MOF degradation while also defining the limits of what fixed-window low-loss EELS can assign without independent chemical-state validation.