Open AccessVibrational Modes and Terahertz Phenomena of the Large-Cage Zeolitic Imidazolate Framework-71
Author(s) -
Annika F. Möslein,
JinChong Tan
Publication year - 2022
Publication title -
the journal of physical chemistry letters
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 2.563
H-Index - 203
ISSN - 1948-7185
DOI - 10.1021/acs.jpclett.2c00081
Subject(s) - zeolitic imidazolate framework , density functional theory , nanoindentation , materials science , spectroscopy , chemical physics , infrared spectroscopy , terahertz radiation , infrared , molecular vibration , neutron spectroscopy , terahertz spectroscopy and technology , nanotechnology , molecular physics , chemistry , scattering , computational chemistry , neutron scattering , optoelectronics , metal organic framework , molecule , optics , physics , adsorption , composite material , organic chemistry , quantum mechanics
The zeolitic imidazole framework ZIF-71 has the potential to outperform other well-studied metal-organic frameworks due to its intrinsic hydrophobicity and relatively large pore size. However, a detailed description of its complex physical phenomena and structural dynamics has been lacking thus far. Herein, we report the complete assignment of the vibrational modes of ZIF-71 using high-resolution inelastic neutron scattering measurements and synchrotron radiation infrared spectroscopy, corroborated by density functional theory (DFT) calculations. With its 816 atoms per unit cell, ZIF-71 is the largest system yet for which frequency calculations have been accomplished employing the CRYSTAL17 DFT code. We discover low-energy terahertz dynamics such as gate-opening and shearing modes that are central to the functions and stability of the ZIF-71 framework structure. Nanoscale analytical methods based on atomic force microscopy (near-field infrared spectroscopy and AFM nanoindentation) further unravel the local chemical and mechanical properties of ZIF-71 single crystals.