A Thermodynamically Consistent Approach to Molecular Simulations of Adsorption-Induced Deformation and Structural Transitions in MOFs

IF 5.8 1区化学 Q2 CHEMISTRY, PHYSICAL

Journal of Chemical Theory and Computation Pub Date : 2026-10-07 DOI:10.1021/acs.jctc.6c01243

Nicholas J. Corrente,Kaelyn Chang,Muhtasim Noor,Alexander V. Neimark

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Abstract

Abstract Flexible metal–organic frameworks (MOFs) exhibit coupled adsorption-deformation behavior that cannot be captured in molecular detail by conventional rigid-framework simulations. We present an iterative hybrid GCMC/MD methodology that explicitly couples grand canonical Monte Carlo sampling of adsorbate configurations with isothermal–isobaric molecular dynamics relaxation of the framework structure, using a Metropolis acceptance criterion in the osmotic ensemble to ensure thermodynamic consistency. Applied to argon adsorption on ZIF-8 at 87.3 K, the method quantitatively reproduces the experimental stepped isotherm characteristic of the gate-opening transition between low pressure (LP) and high pressure (HP) conformations and predicts nonmonotonic strain isotherm with initial contraction (∼0.5%) at low loadings followed by expansion (∼0.7%) during gate-opening. In addition, the elastic modulus variation upon loading is calculated from the volume fluctuations. The simulations reveal and quantify the molecular mechanism of gate-opening through cooperative linker reorientation from a unimodal swing angle distribution centered at 0° to a bimodal distribution peaked at ± 23°. The proposed approach is computationally efficient, yielding converged strain and compressibility isotherms within an accessible number of iterations, and provides a general framework for predicting adsorption-induced structural transitions in flexible porous materials without a priori knowledge of end point structures.

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mof吸附诱导变形和结构转变分子模拟的热力学一致性方法

柔性金属有机框架（mof）表现出耦合的吸附变形行为，这是传统的刚性框架模拟无法捕捉到的分子细节。我们提出了一种迭代混合GCMC/MD方法，该方法明确地将吸附质构型的大正则蒙特卡罗采样与框架结构的等温-等压分子动力学松弛耦合起来，在渗透系综中使用Metropolis接受准则来确保热力学一致性。应用于ZIF-8在87.3 K下的氩气吸附，该方法定量再现了低压（LP）和高压（HP）构象之间的开门过渡的实验阶梯等温线特征，并预测了开门过程中低负荷初始收缩（~ 0.5%）和膨胀（~ 0.7%）的非单调应变等温线。此外，根据体积波动计算了加载时弹性模量的变化。模拟结果揭示并量化了从以0°为中心的单峰摆动角分布到以±23°为峰值的双峰摆动角分布的分子机制。所提出的方法计算效率高，在可访问的迭代次数内产生收敛的应变和压缩等温线，并为预测柔性多孔材料中吸附引起的结构转变提供了一般框架，而无需先验的终点结构知识。

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来源期刊

Journal of Chemical Theory and Computation 化学-物理：原子、分子和化学物理

CiteScore

9.90

自引率

16.40%

发文量

568

审稿时长

1 months

期刊介绍： The Journal of Chemical Theory and Computation invites new and original contributions with the understanding that, if accepted, they will not be published elsewhere. Papers reporting new theories, methodology, and/or important applications in quantum electronic structure, molecular dynamics, and statistical mechanics are appropriate for submission to this Journal. Specific topics include advances in or applications of ab initio quantum mechanics, density functional theory, design and properties of new materials, surface science, Monte Carlo simulations, solvation models, QM/MM calculations, biomolecular structure prediction, and molecular dynamics in the broadest sense including gas-phase dynamics, ab initio dynamics, biomolecular dynamics, and protein folding. The Journal does not consider papers that are straightforward applications of known methods including DFT and molecular dynamics. The Journal favors submissions that include advances in theory or methodology with applications to compelling problems.