<i>In Situ</i> Observation of Gas Adsorption onto ZIF-8 Using Terahertz Waves

Tanno, Takenori; Watanabe, Yudai; Umeno, Kyoko; Matsuoka, Atsushi; Matsumura, Hirotoshi; Odaka, Masafumi; Ogawa, Norio

doi:10.1021/acs.jpcc.7b04833

Cited by 21 publications

(19 citation statements)

References 24 publications

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“…2.0 THz (infrared active), has been controversial. 9,29 While a later study has claimed the spectral assignment by Tan et al 29 to be the correct one, 30 the results of the present study clearly…”

Section: Spectroscopic Fingerprint Of Mechanical Softening On Compressupporting

confidence: 56%

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

et al. 2018

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The identification and characterization of low-frequency vibrational motions of metalorganic frameworks (MOFs) allows for a better understanding of their mechanical and structural response upon perturbation by external stimuli such as temperature, pressure, and adsorption. Here, we describe the combination of an experimental temperatureand pressure-dependent terahertz spectroscopy system with quantum mechanical simulations to measure and assign specific low-frequency vibrational modes that directly drive the mechanochemical properties of this important class of porous materials. More specifically, those intense spectral features in the terahertz region of the vibrational spectrum of ZIF-8 are identified, which are directly connected to its mechanochemical response. In particular, the mechanical compressibility of pristine ZIF-8 is found to follow a peculiar non-linear trend upon pressure: its bulk modulus initially increases up to 0.1 GPa and decreases at higher pressures, which is simultaneously reflected in the terahertz vibrational spectra. This work highlights the interplay between structural, vibrational, and mechanochemical phenomena, all of which are key to the effective exploitation of MOFs. The importance of terahertz vibrational motions on the function of MOFs is demonstrated, and a method presented for their measurement and interpretation, which can be applied widely to any supramolecular material.

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Section: Spectroscopic Fingerprint Of Mechanical Softening On Compressupporting

confidence: 56%

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

et al. 2018

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“…[7][8][9][10] On the other hand, the complex and largeamplitude motions occurring at terahertz frequencies have recently been related to a wide-variety of bulk phenomena, for example phase transformations, 11,12 mechanical responses, 5,13,14 electron-phonon coupling, 15,16 and gas-capture in porous mate-rials. 17,18 Unfortunately, the factors that make terahertz spectroscopy a valuable analytical technique simultaneously lead to one of its biggest challenges -the interpretation of experimental results. Unlike mid-infrared (mid-IR) methods, such as Fourier transform infrared spectroscopy (FTIR) and mid-IR Raman scattering, there do not exist any functional-group specific transitions at terahertz frequencies.…”

Section: Introductionmentioning

confidence: 99%

The Necessity of Periodic Boundary Conditions for the Accurate Calculation of Crystalline Terahertz Spectra

Banks¹,

burgess²,

Ruggiero

2020

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Terahertz vibrational spectroscopy has emerged as a powerful spectroscopic technique, providing valuable information regarding long-range interactions -- and associated collective dynamics -- occurring in solids. However, the terahertz sciences are relatively nascent, and there have been significant advances over the last several decades that have profoundly influenced the interpretation and assignment of experimental terahertz spectra. Specifically, because there do not exist any functional group or material-specific terahertz transitions, it is not possible to interpret experimental spectra without additional analysis, specifically, computational simulations. Over the years simulations utilizing periodic boundary conditions have proven to be most successful for reproducing experimental terahertz dynamics, due to the ability of the calculations to accurately take long-range forces into account. On the other hand, there are numerous reports in the literature that utilize gas phase cluster geometries, to varying levels of apparent success. This perspective will provide a concise introduction into the terahertz sciences, specifically terahertz spectroscopy, followed by an evaluation of gas phase and periodic simulations for the assignment of crystalline terahertz spectra, highlighting potential pitfalls and good practice for future endeavors.

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“…Low-frequency (terahertz) vibrational dynamics have been shown to be one of the major factors that dictate the properties of condensed phase materials, ranging from thermodynamic to mechanical phenomena [1,2]. Additionally, a number of recent investigations have suggested that terahertz motions, which often involve large amplitude displacements of entire molecules, play a vital role in the proper functioning of materials [3][4][5][6][7][8]. However, the dependence of the low-frequency vibrations on both the intramolecular and intermolecular potential energy hypersurfaces leads to unique spectral fingerprints, which cannot be interpreted without additional analysis [9].…”

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confidence: 99%

Uncovering the Connection Between Low-Frequency Dynamics and Phase Transformation Phenomena in Molecular Solids

et al. 2018

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The low-frequency motions of molecules in the condensed phase have been shown to be vital to a large number of physical properties and processes. However, in the case of disordered systems, it is often difficult to elucidate the atomic-level details surrounding these phenomena. In this work, we have performed an extensive experimental and computational study on the molecular solid camphor, which exhibits a rich and complex structure-dynamics relationship, and undergoes an order-disorder transition near ambient conditions. The combination of x-ray diffraction, variable temperature and pressure terahertz time-domain spectroscopy, ab initio molecular dynamics, and periodic density functional theory calculations enables a complete picture of the phase transition to be obtained, inclusive of mechanistic, structural, and thermodynamic phenomena. Additionally, the low-frequency vibrations of a disordered solid are characterized for the first time with atomic-level precision, uncovering a clear link between such motions and the phase transformation. Overall, this combination of methods allows for significant details to be obtained for disordered solids and the associated transformations, providing a framework that can be directly applied for a wide range of similar systems.

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In Situ Observation of Gas Adsorption onto ZIF-8 Using Terahertz Waves

Cited by 21 publications

References 24 publications

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy

The Necessity of Periodic Boundary Conditions for the Accurate Calculation of Crystalline Terahertz Spectra

Uncovering the Connection Between Low-Frequency Dynamics and Phase Transformation Phenomena in Molecular Solids

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