The union of persistent IR hole burning and Fourier-transform IR techniques is used to identify a new type of photophysical vibrational hole-burning center. The persistent signature for matrix-isolated CN(-) complexes in alkali-halide crystals is similar to that found for photochemical hole burning in solids.
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http://dx.doi.org/10.1364/ol.11.000428 | DOI Listing |
Molecules
February 2024
Faculty of Chemistry, University of Wroclaw, F. Joliot-Curie 14, 50-383 Wrocław, Poland.
Photochemical reactions of salicylhydroxamic acid were induced using tunable UV laser radiation followed by FTIR spectroscopy. Four pairs of co-products were experimentally found to appear in the photolysis: CH(OH)NCO⋯HO (1), CH(OH)C(O)N⋯HO (2), CH(OH)⋯HNCO (3), and CH(OH)NHOH⋯CO (4). The comparison of the theoretical spectra with the experimental ones allowed us to determine the structures of the complexes formed in the matrices.
View Article and Find Full Text PDFJ Phys Chem A
June 2022
Department of Chemistry, Lomonosov Moscow State University, Moscow 119991, Russia.
The NH···CO complex can be considered an important building block for cold synthetic astrochemistry leading to the formation of complex organic molecules, including key prebiotic species. In this work, we have studied the radiation-induced transformations of this complex in Ar, Kr, and Xe matrices using FTIR spectroscopy. On the basis of comparison with the quantum chemical calculations at the CCSD(T)/L2a_3 level of theory, it was found that the initial complex had the configuration with hydrogen bonding through the carbon atom of CO.
View Article and Find Full Text PDFChem Commun (Camb)
November 2021
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysts and Innovative Materials, Fudan University, Shanghai 200433, China.
By high-vacuum flash pyrolysis of bis(trifluoromethyl)disulfane oxide (CFS(O)SCF) at 400 °C, the elusive trifluoromethylthiyl radical (CFS˙) has been efficiently generated in the gas phase. Subsequent isolation of CFS˙ in cryogenic matrixes (Ne, Ar, and N) allows a first time characterization with IR and UV-vis spectroscopy by combining with computations at the CCSD(T)/aug--pV(T + d)Z level. In addition to the photo-induced sulfur atom transfer (SAT) from CFS˙ to N and CO and the isomerization to ˙CFSF, the O-oxidation the intermediacy of the novel thiylperoxy radical CFSOO˙ has been observed.
View Article and Find Full Text PDFNanoscale
June 2019
School of Physics, Huazhong University of Science and Technology, Luoyu Road 1037, Wuhan, 430074, People's Republic of China.
Single nanoscopic emitters embedded in the crystalline matrix have become a valuable resource for emerging nanophotonics and quantum technologies. The generally anisotropic nature of the matrix strongly affects the emission properties of the quantum emitters, in particular, when the matrix is assembled in nanophotonic structures. We report on rigorous analysis and engineering of spontaneous emission from single emitters coupled to nanoantenna and planar anisotropic antenna structures.
View Article and Find Full Text PDFPhys Chem Chem Phys
April 2019
International Centre for Quantum and Molecular Structures, Department of Physics, College of Sciences, Shanghai University, 99 Shangda Road, Shanghai, 200444, China.
Conformational changes of the monomeric safrole (5-(2-propenyl)-1,3-benzodioxole) isolated in low temperature xenon matrices were induced thermally or using narrow-band UV radiation. The rotation of the allyl group taking place in the studied matrices was followed by FTIR spectroscopy. Safrole represents a challenging example of a flexible molecule highlighting the importance of dispersion interactions and anharmonic effects in the structural, spectroscopic and energetic analysis.
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