Elucidating the vibrational fingerprint of the flexible metal-organic framework MIL-53(Al) using a combined experimental/computational approach
- Author
- Alexander Hoffman (UGent) , Louis Vanduyfhuys (UGent) , Irena Nevjestic (UGent) , Jelle Wieme (UGent) , Sven Rogge (UGent) , Hannes Depauw (UGent) , Pascal Van Der Voort (UGent) , Henk Vrielinck (UGent) and Veronique Van Speybroeck (UGent)
- Organization
- Abstract
- In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable determination of the theoretical Raman spectrum of the closed-and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed-and large-pore phases, indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.
- Keywords
- FUNCTIONAL PERTURBATION-THEORY, DIELECTRIC-PROPERTIES, CANONICAL ENSEMBLE, FTIR SPECTROSCOPY, CO2 ADSORPTION, SCALE FACTORS, DYNAMICS, PHASE, SOLIDS, SPACE
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Citation
Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-8548363
- MLA
- Hoffman, Alexander et al. “Elucidating the Vibrational Fingerprint of the Flexible Metal-organic Framework MIL-53(Al) Using a Combined Experimental/computational Approach.” JOURNAL OF PHYSICAL CHEMISTRY C 122.5 (2018): 2734–2746. Print.
- APA
- Hoffman, A., Vanduyfhuys, L., Nevjestic, I., Wieme, J., Rogge, S., Depauw, H., Van Der Voort, P., et al. (2018). Elucidating the vibrational fingerprint of the flexible metal-organic framework MIL-53(Al) using a combined experimental/computational approach. JOURNAL OF PHYSICAL CHEMISTRY C, 122(5), 2734–2746.
- Chicago author-date
- Hoffman, Alexander, Louis Vanduyfhuys, Irena Nevjestic, Jelle Wieme, Sven Rogge, Hannes Depauw, Pascal Van Der Voort, Henk Vrielinck, and Veronique Van Speybroeck. 2018. “Elucidating the Vibrational Fingerprint of the Flexible Metal-organic Framework MIL-53(Al) Using a Combined Experimental/computational Approach.” Journal of Physical Chemistry C 122 (5): 2734–2746.
- Chicago author-date (all authors)
- Hoffman, Alexander, Louis Vanduyfhuys, Irena Nevjestic, Jelle Wieme, Sven Rogge, Hannes Depauw, Pascal Van Der Voort, Henk Vrielinck, and Veronique Van Speybroeck. 2018. “Elucidating the Vibrational Fingerprint of the Flexible Metal-organic Framework MIL-53(Al) Using a Combined Experimental/computational Approach.” Journal of Physical Chemistry C 122 (5): 2734–2746.
- Vancouver
- 1.Hoffman A, Vanduyfhuys L, Nevjestic I, Wieme J, Rogge S, Depauw H, et al. Elucidating the vibrational fingerprint of the flexible metal-organic framework MIL-53(Al) using a combined experimental/computational approach. JOURNAL OF PHYSICAL CHEMISTRY C. 2018;122(5):2734–46.
- IEEE
- [1]A. Hoffman et al., “Elucidating the vibrational fingerprint of the flexible metal-organic framework MIL-53(Al) using a combined experimental/computational approach,” JOURNAL OF PHYSICAL CHEMISTRY C, vol. 122, no. 5, pp. 2734–2746, 2018.
@article{8548363,
abstract = {In this work, mid-infrared (mid-IR), far-IR, and Raman spectra are presented for the distinct (meta)stable phases of the flexible metal-organic framework MIL-53(Al). Static density functional theory (DFT) simulations are performed, allowing for the identification of all IR-active modes, which is unprecedented in the low-frequency region. A unique vibrational fingerprint is revealed, resulting from aluminum-oxide backbone stretching modes, which can be used to clearly distinguish the IR spectra of the closed- and large-pore phases. Furthermore, molecular dynamics simulations based on a DFT description of the potential energy surface enable determination of the theoretical Raman spectrum of the closed-and large-pore phases for the first time. An excellent correspondence between theory and experiment is observed. Both the low-frequency IR and Raman spectra show major differences in vibrational modes between the closed-and large-pore phases, indicating changes in lattice dynamics between the two structures. In addition, several collective modes related to the breathing mechanism in MIL-53(Al) are identified. In particular, we rationalize the importance of the trampoline-like motion of the linker for the phase transition.},
author = {Hoffman, Alexander and Vanduyfhuys, Louis and Nevjestic, Irena and Wieme, Jelle and Rogge, Sven and Depauw, Hannes and Van Der Voort, Pascal and Vrielinck, Henk and Van Speybroeck, Veronique},
issn = {1932-7447},
journal = {JOURNAL OF PHYSICAL CHEMISTRY C},
keywords = {FUNCTIONAL PERTURBATION-THEORY,DIELECTRIC-PROPERTIES,CANONICAL ENSEMBLE,FTIR SPECTROSCOPY,CO2 ADSORPTION,SCALE FACTORS,DYNAMICS,PHASE,SOLIDS,SPACE},
language = {eng},
number = {5},
pages = {2734--2746},
title = {Elucidating the vibrational fingerprint of the flexible metal-organic framework MIL-53(Al) using a combined experimental/computational approach},
url = {http://dx.doi.org/10.1021/acs.jpcc.7b11031},
volume = {122},
year = {2018},
}
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