3 years ago

Elucidating the Vibrational Fingerprint of the Flexible Metal–Organic Framework MIL-53(Al) Using a Combined Experimental/Computational Approach

Elucidating the Vibrational Fingerprint of the Flexible
Metal–Organic Framework MIL-53(Al) Using a Combined Experimental/Computational
Approach
Henk Vrielinck, Hannes Depauw, Sven M. J. Rogge, Louis Vanduyfhuys, Irena Nevjestić, Alexander E. J. Hoffman, Jelle Wieme, Pascal Van Der Voort, Veronique Van Speybroeck
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.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b11031

DOI: 10.1021/acs.jpcc.7b11031

You might also like
Discover & Discuss Important Research

Keeping up-to-date with research can feel impossible, with papers being published faster than you'll ever be able to read them. That's where Researcher comes in: we're simplifying discovery and making important discussions happen. With over 19,000 sources, including peer-reviewed journals, preprints, blogs, universities, podcasts and Live events across 10 research areas, you'll never miss what's important to you. It's like social media, but better. Oh, and we should mention - it's free.

  • Download from Google Play
  • Download from App Store
  • Download from AppInChina

Researcher displays publicly available abstracts and doesn’t host any full article content. If the content is open access, we will direct clicks from the abstracts to the publisher website and display the PDF copy on our platform. Clicks to view the full text will be directed to the publisher website, where only users with subscriptions or access through their institution are able to view the full article.