The experimental phase diagram of the CBrCl3+CBr4 system has been determined by means of X-ray powder diffraction and thermal analysis techniques from 200 K to the liquid state. Before melting, the two components have the same orientationally disordered (OD) face-centered cubic phase, and solid-liquid equilibrium is explained by simple isomorphism. The application of multiple crossed isopolymorphism formalism to the low-temperature solid-solid equilibria has enabled the inference of an OD rhombohedral metastable (at normal pressure) phase for CBr4. Experimental determination of the pressure-volume-temperature and construction of the pressure-temperature phase diagrams for CBr4 reveal the existence of a high-pressure phase, the rhombohedral symmetry of which is inferred by means of the thermodynamic assessment of the experimental phase diagram and demonstrated by means of high-pressure neutron diffraction measurements. The procedure used in this work confirms the connection between the appearance of metastable phases at normal pressure and their existence at high-pressure.
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http://dx.doi.org/10.1021/jp806180y | DOI Listing |
J Phys Chem A
October 2024
Department of Chemistry, University of California, Berkeley, California 94720, United States.
A coherent vibrational wavepacket is launched and manipulated in the symmetric stretch (a) mode of CBr, by impulsive stimulated Raman scattering (ISRS) from nonresonant 400 nm laser pump pulses with various peak intensities on the order of tens of 10 W/cm. Extreme ultraviolet (XUV) attosecond transient absorption spectroscopy (ATAS) records the wavepacket dynamics as temporal oscillations in XUV absorption energy at the bromine M 3d edges around 70 eV. The results are augmented by nuclear time-dependent Schrödinger equation simulations.
View Article and Find Full Text PDFInorg Chem
August 2024
Bavarian Research Institute of Experimental Geochemistry and Geophysics (BGI), University of Bayreuth, 95440 Bayreuth, Germany.
Exfoliation of graphite and the discovery of the unique properties of graphene─graphite's single layer─have raised significant attention to layered compounds as potential precursors to 2D materials with applications in optoelectronics, spintronics, sensors, and solar cells. In this work, a new orthorhombic polymorph of yttrium bromide, 16-YBr was synthesized from yttrium and CBr in a laser-heated diamond anvil cell at 45 GPa and 3000 K. The structure of 16-YBr was solved and refined using in situ synchrotron single-crystal X-ray diffraction.
View Article and Find Full Text PDFChempluschem
September 2024
Laboratory of Organic Chemistry, Department of Chemistry, National and Kapodistrian University of Athens, Panepistimiopolis, Athens, 15771, Greece.
In recent years, halogen-bonded complexes (XBCs), in solution, have played a pivotal role in inducing photochemical organic reactions. In this work, we explore the ability of various tertiary amines to act as XB acceptors in the presence of the XB donor CBr by computational and spectroscopic studies. DFT studies clearly showcase the formation of XBCs between the studied tertiary amines and CBr.
View Article and Find Full Text PDFSpectrochim Acta A Mol Biomol Spectrosc
April 2021
School of Chemical Sciences, Indian Association for the Cultivation of Science, Kolkata, West Bengal, India.
Binary complexes of acetone and formic acid with tetrahalomethanes CBr and CCl have been isolated in argon matrix. Spectral shifts in the characteristic ν region of acetone, as well as in the fingerprint regions, are unambiguously assigned to the formation of halogen bond involving one of the halogen atoms on CBr/CCl as donor, and the carbonyl oxygen of acetone as acceptor. The higher magnitude of shifts of ν and the fingerprint vibrations for the CBr complex, as compared to the CCl complex, is consistent with theoretical predictions of higher value of positive electrostatic potential in the "σ-hole" region of the former, and hence its higher susceptibility to halogen bonding.
View Article and Find Full Text PDFChemistry
October 2019
Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio, 43210, USA.
In this work, we report a mechanism by which stereoisomeric and twisted capsules P/M-1 direct their dynamic chirality in the presence of haloalkane guests. The capsule comprises a static, but twisted, cage that is linked to a dynamic tris(2-pyridylmethyl)amine (TPA) lid at its top. From the results of experimental (NMR spectroscopy and X-ray crystallography) and computational (DFT) studies, the TPA lid was shown to assume clockwise (+) and counterclockwise (-) folds with diastereomeric (but racemic) capsules M-1(+) and M-1(-) interconverting at a rapid rate (ΔG =9.
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