Structural, electronic, and optical properties of crystalline iodoform under high pressure: A first-principles study

Bao, Gang; Duan, Defang; Tian, Fubo; Wang, Liancheng; Liu, Bingbing; Cui, Tian

doi:10.1063/1.3528728

Cited by 7 publications

(3 citation statements)

References 35 publications

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“…In this condensed phase, HCl-HCl contacts have an L-shaped geometry, with the H-Cl bond axis of one molecule perpendicular to the other one. A similar herringbone pattern is also observed in solid X 2 (X, halogen) 25,26 . Fig.…”

Section: Hcl: a Brief Revisit Of The Pressure-induced Symmetrisation ...supporting

confidence: 75%

Emergence of novel hydrogen chlorides under high pressure

Zeng

Duan

et al. 2017

Phys. Chem. Chem. Phys.

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HCl is a textbook example of a polar covalent molecule, and has a wide range of industrial applications. Inspired by the discovery of unexpected stable sodium and potassium chlorides, we performed systematic ab initio evolutionary searches for all stable compounds in the H-Cl system at pressures up to 400 GPa. Besides HCl, four new stoichiometries (HCl, HCl, HCl and HCl) are found to be stable under pressure. Our predictions substantially differ from previous theoretical studies. We evidence a high significance of zero-point energy in determining phase stability. The newly discovered compounds display a rich variety of chemical bonding characteristics. At ambient pressure, H, Cl and HCl molecular crystals are formed by weak intermolecular van der Waals interactions, and adjacent HCl molecules connect with each other to form asymmetric zigzag chains, which become symmetric under high pressure. In HCl, triangular H cations are stabilized by electrostatic interactions with the anionic chloride network. Further increase of pressure drives H dimers to combine with H cations to form H units. We also found chlorine-based Kagomé layers which are intercalated with zigzag HCl chains in HCl. These findings could help to understand how varied bonding features can co-exist and evolve in one compound under extreme conditions.

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Section: Hcl: a Brief Revisit Of The Pressure-induced Symmetrisation ...supporting

confidence: 75%

Emergence of novel hydrogen chlorides under high pressure

Zeng

Duan

et al. 2017

Phys. Chem. Chem. Phys.

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“…Polar and/or non-centrosymmetric crystals of organic materials are highly requested because they can be used as optoelectronic transducers, actuators, ferro-, piezo and pyroelectric materials and for technological applications [1]. Iodoform (CHI 3 ) is a good molecule in this sense, with permanent dipole moment and a rigid molecular arrangement [2].…”

Section: Introductionmentioning

confidence: 99%

The effects of P–T changes on intermolecular interactions in crystal structure of iodoform

Bertolotti

Curetti

Benna

et al. 2013

Journal of Molecular Structure

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“…The only exception is iodoform (CH 3 I) which was studied by powder X-ray diffraction up to 40 GPa, and by Raman spectroscopy up to 22 GPa [27]. Computational studies on the high-pressure transformations of crystals containing tri-and dihalomethane are also scarce, with only CHBr 3 and CHI 3 investigated [38,39]. Table 1.…”

Section: Introductionmentioning

confidence: 99%

Phase Stability of Chloroform and Dichloromethane at High Pressure

2020

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Chloroform (CHCl3) and dichloromethane (CH2Cl2) are model systems for the study of intermolecular interactions, such as hydrogen bonds and halogen–halogen interactions. Here we report a joint computational (density-functional perturbation theory (DFPT) modelling) and experimental (Raman scattering) study on the behaviour of the crystals of these compounds up to a pressure of 32 GPa. Comparing the experimental information on the Raman band positions and intensities with the results of calculations enabled us to characterize the pressure-induced evolution of the crystal structure of both compounds. We find that the previously proposed P63 phase of CHCl3 is in fact a metastable structure, and that up to 32 GPa the ambient-pressure Pnma structure is the ground state polymorph of this compound. For CH2Cl2 we confirm the stability of the ambient-pressure Pbcn structure up to 32 GPa. We show that the high-pressure evolution of the crystal geometry of CHCl3 in the Pnma structure is a result of the subtle balance between dipole–dipole interactions, hydrogen bonds and Cl···Cl contacts. For CH2Cl2 (Pbcn structure) the dipole–dipole interactions and hydrogen bonds are the main factors influencing the pressure-induced changes in the geometry.

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Structural, electronic, and optical properties of crystalline iodoform under high pressure: A first-principles study

Cited by 7 publications

References 35 publications

Emergence of novel hydrogen chlorides under high pressure

Emergence of novel hydrogen chlorides under high pressure

The effects of P–T changes on intermolecular interactions in crystal structure of iodoform

Phase Stability of Chloroform and Dichloromethane at High Pressure

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