A Thermodynamically Consistent Approach to Molecular Simulations of Adsorption-Induced Deformation and Structural Transitions in MOFs
- 1Department of Chemical and Biochemical Engineering, Rutgers University, Piscataway, New Jersey 08854, United States
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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BibTeX
@article{corrente2026thermodynamically,
title = {{A Thermodynamically Consistent Approach to Molecular Simulations of Adsorption-Induced Deformation and Structural Transitions in MOFs}},
author = {Nicholas J. Corrente and Kaelyn Chang and Muhtasim Noor and Alexander V. Neimark},
journal = {Journal of Chemical Theory and Computation},
year = {2026},
month = oct,
doi = {10.1021/acs.jctc.6c01243},
url = {https://doi.org/10.1021/acs.jctc.6c01243},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - A Thermodynamically Consistent Approach to Molecular Simulations of Adsorption-Induced Deformation and Structural Transitions in MOFs
AU - Nicholas J. Corrente
AU - Kaelyn Chang
AU - Muhtasim Noor
AU - Alexander V. Neimark
PY - 2026
DA - 2026/10/07
JO - Journal of Chemical Theory and Computation
DO - 10.1021/acs.jctc.6c01243
UR - https://doi.org/10.1021/acs.jctc.6c01243
AB - 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.
SN - 1549-9618
SN - 1549-9626
ER -