Hydantoin (C(3)H(4)N(2)O(2), 2,4-imidazolidinedione) was isolated in argon matrix at 10 K and its infrared spectrum and unimolecular photochemistry were investigated. The molecular structure of the compound was studied both at the DFT(B3LYP) and MP2 levels of approximation with valence triple- and quadruple-ζ basis sets (6-311++G(d,p); cc-pVQZ). It was concluded that the minima in the potential energy surfaces of the molecule correspond to C(1) symmetry structures. However, the energy barrier separating the two-equivalent-by-symmetry minima stays below their zero-point energy, which makes the C(s) symmetry structure, which separates the two minima, the experimentally relevant one. The electronic structure of the molecule was studied in detail by performing the Natural Bond Orbital analysis of its electronic configuration within the DFT(B3LYP)/cc-pVQZ space. The infrared spectrum of the matrix isolated compound was fully assigned also with help of the theoretically predicted spectrum. Upon irradiation at λ = 230 nm, matrix-isolated hydantoin was found to photofragment into isocyanic acid, CO, and methylenimine.

The structural, vibrational, and photochemical study of 1-methylhydantoin (1-MH, C4H6N2O2) was undertaken by matrix isolation infrared spectroscopy (in argon matrix; 10 K), complemented by quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of approximation. The theoretical calculations yielded the Cs symmetry structure, with planar heavy atom skeleton, as the minimum energy structure on the potential energy surface of the molecule. The electronic structure of this minimum energy structure of 1-MH was then studied in detail by means of the natural bond orbital (NBO) and atoms in molecules (AIM) approaches, allowing for the elucidation of specific characteristics of the molecule's σ and π electronic systems. The infrared spectrum of the matrix-isolated 1-MH was fully assigned, also with the help of the theoretically predicted spectrum of the compound, and its UV-induced unimolecular photochemistry (λ ≥ 230 nm) was investigated. The compound was found to fragment to CO, isocyanic acid, methylenimine, and N-methyl-methylenimine. Finally, a thermal behavior investigation on 1-MH samples was carried out using infrared spectroscopy (10 K until melting), differential scanning calorimetry and polarized light thermal microscopy. A new polymorph of 1-MH was identified. The IR spectra of the different observed phases were recorded and interpreted.

IR-induced reactions in cryogenic matrices and related tunneling-driven processes are surveyed, highlighting the entanglement between the two types of processes.

In this study the geometry optimization of monomeric and dimeric forms (D1, D2, and D3) of hydantoin molecule were done using DFT method employing 6-31++G(d, p) basis set. Harmonic and anharmonic wavenumbers and infrared intensities were computed at the same theory level. Experimental IR spectrum was recorded in the region 400-4000 cm -1 . It has also been characterized by 1 H and 13 C NMR spectrum. The hydrogen bond (HB) interaction of hydantoin was analyzed via dimers of hydantoin. Detailed vibrational wavenumber shifts and all vibrational mode analyses were reported. Total energy distributions (TED, %) calculations were done to characterize the fundamentals.

The Saric ßic ßek howardite meteorite shower consisting of 343 documented stones occurred on September 2, 2015 in Turkey and is the first documented howardite fall. Cosmogenic isotopes show that Saric ßic ßek experienced a complex cosmic-ray exposure history, exposed during~12-14 Ma in a regolith near the surface of a parent asteroid, and that añ 1 m sized meteoroid was launched by an impact 22 AE 2 Ma ago to Earth (as did one-third of all HED meteorites). SIMS dating of zircon and baddeleyite yielded 4550.4 AE 2.5 Ma and 4553 AE 8.8 Ma crystallization ages for the basaltic magma clasts. The apatite U-Pb age of 4525 AE 17 Ma, K-Ar age of~3.9 Ga, and the U,Th-He ages of 1.8 AE 0.7 and 2.6 AE 0.3 Ga are interpreted to represent thermal metamorphic and impact-related resetting ages, respectively. Petrographic; geochemical; and O-, Cr-, and Ti-isotopic studies confirm that Saric ßic ßek belongs to the normal clan of HED meteorites. Petrographic observations and analysis of organic material indicate a small portion of carbonaceous chondrite material in the Saric ßic ßek regolith and organic contamination of the meteorite after a few days on soil. Video observations of the fall show an atmospheric entry at 17.3 AE 0.8 km s À1 from NW; fragmentations at 37, 33, 31, and 27 km altitude; and provide a pre-atmospheric orbit that is the first dynamical link between the normal HED meteorite clan and the inner Main Belt. Spectral data indicate the similarity of Saric ßic ßek with the Vesta asteroid family (V-class) spectra, a group of asteroids stretching to delivery resonances, which includes (4) Vesta. Dynamical modeling of meteoroid delivery to Earth shows that the complete disruption of ã 1 km sized Vesta family asteroid or a~10 km sized impact crater on Vesta is required to provide sufficient meteoroids ≤4 m in size to account for the influx of meteorites from this HED clan. The 16.7 km diameter Antionia impact crater on Vesta was formed on terrain of the same age as given by the 4 He retention age of Saric ßic ßek. Lunar scaling for crater production to crater counts of its ejecta blanket show it was formed~22 Ma ago.A field expedition to the area was conducted by the

The molecular structure, vibrational spectra and photochemistry of 5-methylhydantoin (CHNO; 5-MH) were studied by matrix isolation infrared spectroscopy and theoretical calculations at the DFT(B3LYP)/6-311++G(d,p) theory level. The natural bond orbital (NBO) analysis approach was used to study in detail the electronic structure of the minimum energy structure of 5-MH, namely the specific characteristics of the σ and π electronic systems of the molecule and the stabilizing orbital interactions. UV irradiation of 5-MH isolated in argon matrix resulted in its photofragmentation through a single photochemical pathway, yielding isocyanic acid, ethanimine, and carbon monoxide, thus following a pattern already observed before for the parent hydantoin and 1-methylhydantoin molecules. The investigation of the thermal properties of 5-MH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy. Four different polymorphs of 5-MH were identified. The crystal structure of one of the polymorphs, for which it was possible to grow up suitable crystals, was determined by X-ray diffraction (XRD). Two of the additional polymorphs were characterized by powder XRD, which confirmed the molecules pack in different crystallographic arrangements.

The conformational space of 5-acetic acid hydantoin {5AAH; [2-(2,5dioxoimidazolidin-4-yl)acetic acid]} was investigated by quantum chemical calculations performed at the DFT(B3LYP)/6-311++G(d,p) level of theory. A total of 13 conformers were located in the potential energy surface of the molecule, 6 of them bearing the carboxylic group in the cis arrangement (O=C-O-H dihedral equal to ~0º) and the other 7 possessing this group in the trans configuration (O=C-O-H dihedral equal to ~180º). The most stable conformer (cis-I) was trapped from the gas phase into a low temperature argon matrix (10 K), and its infrared spectrum was fully assigned, also with help of results of normal coordinates' analysis based on the DFT computed vibrational data. The electronic structure of this conformer was analyzed by using the Natural Bond Orbital (NBO) method.The investigation of the thermal properties of 5-AAH was undertaken by differential scanning calorimetry (DSC), polarized light thermal microscopy (PLTM) and Raman spectroscopy, allowing identification of five different polymorphs. Very interestingly, in the room temperature stable polymorph the molecular units of 5-AAH assume the geometry of the highest-energy conformer predicted by the calculations for the isolated molecule.

The first observation of the higher-energy conformer of tribromoacetic acid (trans-TBAA) is reported. The conformer was produced in cryogenic matrices (Ar, Kr, and N) by in situ selective narrowband near-infrared excitation of the lower-energy cis-TBAA conformer and characterized both structurally and vibrationally. The novel trans-TBAA conformer is shown to spontaneously decay to the most stable cis-TBAA form in all studied matrix media, by tunneling, and the measured decay rates in the different matrices were compared with those of the trans conformers of other carboxylic acids in similar experimental conditions. In the N matrix, where trans-TBAA establishes a specific stabilizing intermolecular interaction with the host N molecules via its OH group and is about 11 times more stable than in rare gas matrices, the effect of changing the irradiation wavenumber within the 2νOH absorption profile was investigated in detail. An interesting phenomenon of matrix-site changing mediated by conformational conversion was observed in the N matrix: vibrational excitation of cis-TBAA in the 2νOH wavenumber range predominantly converts the molecules located in a specific "matrix site" into trans-TBAA; then, relaxation (by tunneling) of the produced higher-energy conformer back to the cis form populates almost exclusively another "matrix site." The experimental studies received support from quantum chemistry calculations, which allowed a detailed characterization of the relevant regions of the potential energy surface of the molecule and the detailed assignment of the infrared spectra of the two conformers in the various matrices.