This study uses in situ vibrational spectroscopy to probe nitrogen adsorption to porous carbon materials, including single-wall carbon nanotubes and Maxsorb super-activated carbon, demonstrating how the nitrogen Raman stretch mode is perturbed by adsorption. In all porous carbon samples upon N2 physisorption in the mesopore filling regime, the N2 Raman mode downshifts by ∼2 cm-1, a downshift comparable to liquid N2. The relative intensity of this mode increases as pressure is increased to saturation, and trends in the relative intensity parallel the volumetric gas adsorption isotherm. This mode with ∼2 cm-1 downshift is thus attributed to perturbations arising due to N2-N2 interactions in a condensed film. The mode is also observed for the activated carbon at 298 K, and the relative intensity once again parallels the gas adsorption isotherm. For select samples, a mode with a stronger downshift (>4 cm-1) is observed, and the stronger downshift is attributed to stronger N2-carbon surface interactions. Simulations for a N2 surface film support peak assignments. These results suggest that N2 vibrational spectroscopy could provide an indication of the presence or absence of porosity for very small quantities of samples.
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http://dx.doi.org/10.1039/c8cp01790e | DOI Listing |
Nanotechnology
January 2025
Walker Department of Mechanical Engineering, The University of Texas at Austin, 204 E. Dean Keeton St., Austin, Texas, 78712-1139, UNITED STATES.
Sapphire is an attractive material in photonic, optoelectronic, and transparent ceramic applications that stand to benefit from surface functionalization effects stemming from micro/nanostructures. Here we investigate the use of ultrafast lasers for fabricating nanostructures in sapphire by exploring the relationship between irradiation parameters, morphology change, and selective etching. In this approach an ultrafast laser pulse is focused on the sapphire substrate to change the crystalline morphology to amorphous or polycrystalline, which is characterized by examining different vibrational modes using Raman spectroscopy.
View Article and Find Full Text PDFNano Lett
January 2025
Center for High Pressure Science and Technology Advanced Research, Shanghai 201203, P. R. China.
The vibron behavior of hydrogen bears significant importance for understanding the phases of solid hydrogen under high pressure. In this work, we reveal an unusual high-pressure behavior of hydrogen confined within nanopores through a combination of experimental measurements and theoretical calculations. The nanoconfined hydrogen molecules retain an hcp lattice up to 170 GPa, yet significant deviations from the vibrational characteristics of bulk hydrogen are observed in the primary vibrons of both Raman and infrared spectra.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
University of Göttingen, Institute for Physical Chemistry, Tammannstraße 6, 37077,Göttingen Germany.
Rotational spectroscopy is an excellent tool for structure determination, which can provide additional insights into local electronic structure by investigating the hyperfine pattern due to nuclear quadrupole coupling. Jet-cooled molecules are good experimental benchmark targets for electronic structure calculations, as they are free of environmental effects. We report the rotational spectra of 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, and 4-chlorobenzaldehyde, including a complete experimental description of the nuclear quadrupole coupling constants, which were previously not experimentally determined.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, Brown University, Providence, Rhode Island 02912, United States.
The cyano-cyclopentadiene molecule (CN-CH) has attracted significant interest since its detection in the interstellar medium, but the radical (CN-CH) and anionic (CN-CH) forms of cyano-cyclopentadiene have not been studied. The cyano-cyclopentadienyl radical (CN-Cp) has a strong dipole moment, rendering it an ideal system for vibrational and rotational spectroscopy. We report an investigation of the cryogenically cooled cyano-cyclopentadienide anion (CN-Cp) using high-resolution photoelectron imaging, photodetachment spectroscopy, and resonant photoelectron imaging.
View Article and Find Full Text PDFJ Phys Chem A
January 2025
Department of Chemistry, University of California, Davis, One Shields Ave., Davis, California 95616, United States.
Combustion and pyrolysis processes of allene and propyne are known to involve radicals with the structural formula CH, the most stable of which is the classic resonance-stabilized allyl radical. In addition to allyl, four other isomers of CH are possible: the propene derivatives -1-propenyl, -1-propenyl, and 2-propenyl, as well as the cyclopropane derivative cyclopropyl. Among these 5 species, the allyl radical has been extensively studied both theoretically and spectroscopically; however, little is known about the spectroscopy of the cyclopropyl radical, and virtually no experimental spectroscopic data are available for the remaining three.
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