Investigation of CO2 Orientational Dynamics through Simulated NMR Line Shapes**

Patrick Melix; Thomas Heine

doi:10.1002/cphc.202100489

Investigation of CO₂ Orientational Dynamics through Simulated NMR Line Shapes**

Patrick Melix, Thomas Heine

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

2 Citations (Scopus)

Abstract

The dynamics of carbon dioxide in third generation (i. e., flexible) Metal-Organic Frameworks (MOFs) can be experimentally observed by ¹³C NMR spectroscopy. The obtained line shapes directly correlate with the motion of the adsorbed CO₂, which in turn are readily available from classical molecular dynamics (MD) simulations. In this article, we present our publicly available implementation of an algorithm to calculate NMR line shapes from MD trajectories in a matter of minutes on any current personal computer. We apply the methodology to study an effect observed experimentally when adsorbing CO₂ in different samples of the pillared layer MOF Ni₂(ndc)₂(dabco) (ndc=2,6-naphthalene-dicarboxylate, dabco=1,4-diazabicyclo-[2.2.2]-octane), also known as DUT-8(Ni). In ¹³C NMR experiments of adsorbed CO₂ in this MOF, small (rigid) crystals result in narrower NMR line shapes than larger (flexible) crystals. The reasons for the higher mobility of CO₂ inside the smaller crystals is unknown. Our ligand field molecular mechanics simulations provide atomistic insight into the effects visible in NMR experiments with limited computational effort.

Original language	English
Pages (from-to)	2336-2341
Number of pages	6
Journal	ChemPhysChem
Volume	22
Issue number	22
DOIs	https://doi.org/10.1002/cphc.202100489
Publication status	Published - 2021 Nov 18

Bibliographical note

Funding Information:
This work was funded by DFG through FOR2433. PM acknowledges funding by the Humboldt foundation through a Feodor-Lynen fellowship during writing of this article. We thank ZIH Dresden for providing computational resources. We gratefully acknowledge the fruitful discussions with Dr. S. Ehrling, M. Rauche and especially Prof. E. Brunner, who initiated the investigation and provided insights, experimental data and feedback for the manuscript. Open Access funding enabled and organized by Projekt DEAL.

Funding Information:
This work was funded by DFG through FOR2433. PM acknowledges funding by the Humboldt foundation through a Feodor‐Lynen fellowship during writing of this article. We thank ZIH Dresden for providing computational resources. We gratefully acknowledge the fruitful discussions with Dr. S. Ehrling, M. Rauche and especially Prof. E. Brunner, who initiated the investigation and provided insights, experimental data and feedback for the manuscript. Open Access funding enabled and organized by Projekt DEAL.

Publisher Copyright:
© 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH

All Science Journal Classification (ASJC) codes

Atomic and Molecular Physics, and Optics
Physical and Theoretical Chemistry

Access to Document

10.1002/cphc.202100489

Cite this

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title = "Investigation of CO2 Orientational Dynamics through Simulated NMR Line Shapes**",

abstract = "The dynamics of carbon dioxide in third generation (i. e., flexible) Metal-Organic Frameworks (MOFs) can be experimentally observed by 13C NMR spectroscopy. The obtained line shapes directly correlate with the motion of the adsorbed CO2, which in turn are readily available from classical molecular dynamics (MD) simulations. In this article, we present our publicly available implementation of an algorithm to calculate NMR line shapes from MD trajectories in a matter of minutes on any current personal computer. We apply the methodology to study an effect observed experimentally when adsorbing CO2 in different samples of the pillared layer MOF Ni2(ndc)2(dabco) (ndc=2,6-naphthalene-dicarboxylate, dabco=1,4-diazabicyclo-[2.2.2]-octane), also known as DUT-8(Ni). In 13C NMR experiments of adsorbed CO2 in this MOF, small (rigid) crystals result in narrower NMR line shapes than larger (flexible) crystals. The reasons for the higher mobility of CO2 inside the smaller crystals is unknown. Our ligand field molecular mechanics simulations provide atomistic insight into the effects visible in NMR experiments with limited computational effort.",

author = "Patrick Melix and Thomas Heine",

note = "Funding Information: This work was funded by DFG through FOR2433. PM acknowledges funding by the Humboldt foundation through a Feodor-Lynen fellowship during writing of this article. We thank ZIH Dresden for providing computational resources. We gratefully acknowledge the fruitful discussions with Dr. S. Ehrling, M. Rauche and especially Prof. E. Brunner, who initiated the investigation and provided insights, experimental data and feedback for the manuscript. Open Access funding enabled and organized by Projekt DEAL. Funding Information: This work was funded by DFG through FOR2433. PM acknowledges funding by the Humboldt foundation through a Feodor‐Lynen fellowship during writing of this article. We thank ZIH Dresden for providing computational resources. We gratefully acknowledge the fruitful discussions with Dr. S. Ehrling, M. Rauche and especially Prof. E. Brunner, who initiated the investigation and provided insights, experimental data and feedback for the manuscript. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: {\textcopyright} 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH",

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N2 - The dynamics of carbon dioxide in third generation (i. e., flexible) Metal-Organic Frameworks (MOFs) can be experimentally observed by 13C NMR spectroscopy. The obtained line shapes directly correlate with the motion of the adsorbed CO2, which in turn are readily available from classical molecular dynamics (MD) simulations. In this article, we present our publicly available implementation of an algorithm to calculate NMR line shapes from MD trajectories in a matter of minutes on any current personal computer. We apply the methodology to study an effect observed experimentally when adsorbing CO2 in different samples of the pillared layer MOF Ni2(ndc)2(dabco) (ndc=2,6-naphthalene-dicarboxylate, dabco=1,4-diazabicyclo-[2.2.2]-octane), also known as DUT-8(Ni). In 13C NMR experiments of adsorbed CO2 in this MOF, small (rigid) crystals result in narrower NMR line shapes than larger (flexible) crystals. The reasons for the higher mobility of CO2 inside the smaller crystals is unknown. Our ligand field molecular mechanics simulations provide atomistic insight into the effects visible in NMR experiments with limited computational effort.

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