Infrared spectra of urea isolated in a solid argon matrix

Pure monomeric urea molecules, free of contamination with decomposition products, have been obtained by sublimation of solid urea at ca 30°C and isolating in argon at ca 10K. Very high dilution is required to obtain the pure monomer which shows many spectral features different from that previously reported by King [Spectrochim. Acta28A, 165 (1972)]. The i.r. spectrum of the deutero-analogue has also been measured.     

Infrared spectra and electronic structures of agostic uranium methylidene molecules

Through reactions of laser-ablated uranium atoms with methylene halides CH2XY (XY = F2, FCl, and Cl2), a series of new actinide methylidene molecules CH2UF2, CH2UFCl, and CH2UCl2 are formed as the major products. The identification of these complexes has been accomplished via matrix infrared spectra, isotopic substitution, and relativistic density functional calculations of the vibrational frequencies and infrared intensities. Density functional calculations using the generalized gradient approach (PW91) show that these CH2UXY methylidene complexes prefer highly distorted agostic structures rather than the ethylene-like symmetric structures. The calculated agostic angles ([angle]H-C-U) are around 89 degrees for all the three uranium complexes, and the predicted vibrational modes and isotopic shifts agree well with experimental values. Electronic structure calculations reveal that these U(IV) molecules all have strong C=U double bonds in the triplet ground states with 5f (2) configurations. The calculated bond lengths and bond energies indicate that the C=U double bonds are slightly weaker in the fluoride species than in the chloride species because of the radial contraction of the U (6d) orbitals by the inductive effect of the fluorine substituent. The agostic uranium methylidene complexes are compared with analogous transition metal and thorium complexes, which reveal interesting differences in their chemistries.     

Infrared spectra of RuTPP, RuCOTPP, and Ru(CO)2TPP isolated in solid argon

Infrared spectra of unstable species such as CO-free ruthenium tetraphenylporphyrin RuTPP and RuCOTPP (species with vacant coordination sites) isolated in solid argon at 8 K have been recorded. Selective deposition conditions allow the isolation of either RuTPP and RuCOTPP or RuCOTPP and Ru(CO)2TPP. This depends on the preparation conditions of the sample. A specific Ru-CO bending mode has been characterized at 590.1 cm(-1) for Ru(CO)2TPP. The behavior of each vibrational mode of RuTPP, RuCOTPP, and Ru(CO)2TPP has been analyzed. Modes such as gamma8 at 721.3 cm(-1) (out-of-plane stretching mode gamma(Cbeta-H)sym) and nu41 at 1342.8 cm(-1) (nuCalpha-N coupled with deltaCalpha-Cm) reflect the charge transfer in the porphyrin. Indeed, the addition of one or two CO ligands to RuTPP reduces the charge transfer between the metal center and the porphyrin, which appears as an increase in the frequency of the nu41 mode and in a decrease in that of the gamma8 mode.     

Infrared absorption spectra of vinyl radicals isolated in solid Ne

Irradiation of samples of solid Ne near 3.0 K containing ethene (C(2)H(4)) with vacuum ultraviolet radiation at 120 nm from synchrotron yielded new spectral lines at 3141.0, 2953.6, 2911.5, 1357.4, 677.1, 895.3, and 857.0 cm(-1). These features are assigned to alpha-CH stretching (nu(1)), CH(2) antisymmetric stretching (nu(2)), CH(2) symmetric stretching (nu(3)), CH(2)-bending (nu(5)), HCCH cis bending (nu(7)), CH(2) out-of-plane bending (nu(8)), and alpha-CH out-of-plane bending (nu(9)) modes of C(2)H(3), respectively, based on results of (13)C- and D-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict vibrational wavenumbers, IR intensities, and isotopic ratios of vinyl radical that agree satisfactorily with our experimental results.     

Infrared spectra of cis- and trans-peroxynitrite anion, OONO-, in solid argon

The peroxynitrite anion, of vast importance in biochemistry, is formed in vivo from the reaction of NO and O(-2). Laser ablation of 10 different metal targets with concurrent 7 K codeposition of NO/Ar and O(2)/Ar mixtures gives new metal-independent infrared bands at 1458.3 and 806.1 cm(-)(1), and at 1433.3 and 983.2 cm(-1), in addition to known O(-4) and (NO)(-2) absorptions. The new bands are not observed with CCl(4) added to capture electrons or in O(2) and NO experiments without laser ablation to produce electrons, which identifies new product anions. Based on (15)NO and (18)O(2) isotopic shifts, splitting patterns in mixed isotopic experiments, and comparison with DFT isotopic frequency calculations, the former absorptions are assigned to cis-OONO-, and the latter pair to trans-OONO-, which are isolated from metal cations trapped elsewhere in the matrix. The cis- and trans-peroxynitrite anion isomers are probably formed via the ion-molecule reaction between O(-2)and NO: the O(-2) anion, made by the capture of ablated electrons, is attested by the observation of O(-4). cis- and trans-OONO- are reversibly photoisomerized by visible and near-UV radiation. Collisional stabilization of the OONO- ion-molecule dimer complex during formation of the solid argon matrix appears to be crucial.     

Infrared spectra of phenyl nitrite and phenoxyl radical-nitric oxide complex in solid argon

Infrared spectra and frequency assignment of two isomers of nitrobenzene, namely the phenyl nitrite C6H(5-)ONO molecule and the phenoxyl radical-nitric oxide complex C6H5O-NO, in solid argon are presented. The phenoxyl radical-nitric oxide complex was produced through UV light irradiation of nitrobenzene in low-temperature solid argon matrix. The complex rearranged to the more stable phenyl nitrite molecule on sample annealing. The aforementioned species were identified on the basis of isotopic IR studies with C6H(5-)(15)NO2 and C6D5NO2, as well as density functional theory calculations.     

Infrared spectra of the OH+ and H2O+ cations solvated in solid argon

Infrared spectra of various OH+ and H2O+ isotopomers solvated in solid argon are presented. The OH+ and H2O+ cations were produced by co-deposition of H2O/Ar mixture with high-frequency discharged Ar at 4 K. Detailed isotopic substitution studies confirm the assignments of absorptions at 3054.9 and 3040.0 cm(-1) to the antisymmetric and symmetric H-O-H stretching vibrations of H2O+ and 2979.6 cm(-1) to the O-H stretching vibration of OH+. The frequencies of H2O+ solvated in solid argon are red-shifted, whereas the frequency of OH+ is blue-shifted with respect to the gas-phase fundamentals. On the basis of previous gas-phase studies and quantum chemical calculations, the OH+ and H2O+ cations solvated in solid argon may be regarded as the OH+-Ar5 and H2O+-Ar4 complexes isolated in the argon matrix.     

Electronic absorption and resonance Raman spectra of large linear carbon clusters isolated in solid argon

Neutral and anionic carbon clusters have been generated via a laser-induced graphite-based plasma and deposited in a solid argon matrix. Anionic clusters were formed from neutral clusters by using crossed electron/carbon cluster beams. Thermal annealing (to 36 K) resulted in the aggregation of the smaller carbon species, leading to the formation of long chain neutral and anionic clusters. Spectroscopic measurements in the ultraviolet, visible, near-infrared and infrared regions revealed a series of bands attributable to a homologous set of odd-numbered C5-C29 neutral clusters and even-numbered C6(-)-C36- anionic clusters. Good agreement is found for the band positions of carbon chains containing odd C15-C21 neutrals and even C6(-)-C22- anions, with species previously identified by Maier and coworkers using mass selection or laser vaporization, followed by neon matrix isolation. Resonance Raman frequencies for the neutral C17, C21 and C23 species are shown to be consistent with the above attributions. Density functional theory calculations agree well with the observed bands. It is found that certain low frequency Raman stretching frequencies decrease in a predictable way with increasing chain length. Comparison of the 0(0)0 absorption transitions of the even C18(-)-C36- anionic clusters with the 'unidentified' infrared (UIR) interstellar emission bands suggests that the electronic emission from specific long chain carbon anions may contribute to the some of the UIR bands.     

Infrared spectra and UV-induced photochemistry of methyl aziridine-2-carboxylate isolated in argon and xenon matrices

Methyl aziridine-2-carboxylate (MA2C) has been isolated in low temperature argon and xenon matrices and its structure and photochemistry were studied by FTIR spectroscopy. The reactant as well as the main photoproducts were characterized by comparison of their experimental IR spectra with spectra calculated at the DFT(B3LYP)/6-311++G(d,p) level. The theoretical calculations predicted the existence of two low energy MA2C conformers, differing by the orientation of the OCCN dihedral angle. Both conformers were identified in the studied matrices. Both narrowband tunable and broadband UV irradiations of matrix-isolated MA2C yielded isomerization photoproducts resulting from cleavage of the CC and weakest CN bonds of the aziridine ring. Irradiation with UV laser-light at λ = 235 nm resulted in the formation of the E isomer of methyl 2-(methylimino)-acetate (MMIA) and the Z isomer of methyl 3-iminopropanoate (M3IP). Subsequent irradiation at 290 nm led to observation of new bands resulting from E → Z isomerization of MMIA, while bands due to M3IP remained unchanged. The photoproduced Z isomer of MMIA could be subsequently consumed upon higher-wavelength irradiation (λ = 330 nm). The initially produced MMIA conformer was found to obey the nonequilibrium of excited rotamers (NEER) principle. No photoproducts resulting from the cleavage of the strongest CN bond of the MA2C aziridine ring were observed, nor that of methyl 3-aminoacrylate (M3AA), which could in principle be obtained also by cleavage of the weakest CN bond of the MA2C aziridine ring, but would imply a different H-atom migration simultaneous with the ring opening process. These results indicate that both the differential electronic characteristics of the CN bonds of substituted aziridine rings and the type of required H-atom migration are major factors in determining the specific photochemistries of substituted aziridines. Photofragmentation reactions of MA2C were also observed, through identification of various related products, e.g., acetonitrile, methanol, methane, CO and CO₂.     

Infrared spectra of the sulfenic ester CH3SOCH3 and its photodissociation products in solid argon

UV light irradiation of dimethyl sulfoxide (DMSO) in low temperature solid argon matrix produces sulfenic ester, CH 3SOCH 3, a high energy structural isomer of DMSO. The sulfenic ester molecule further dissociates to the CH 2O-CH 3SH complex under 266 nm laser irradiation. The CH 2S-CH 3OH complex is also formed upon UV light irradiation. The infrared spectra of the aforementioned species are assigned on the basis of isotopic substitutions ( (13)C and deuterium) as well as density functional frequency calculations.     

Infrared spectra of some alkylfurans

The possibility of using the region of the C=C and C-H vibrations of the furan ring for the analysis of the structure of substituted furans and the possibility of determining the structure of the side chain in alkylfurans and alkylbenzofurans have been shown.     

Infrared spectra and theoretical calculations of lithium hydride clusters in solid hydrogen, neon, and argon

A matrix isolation IR study of laser-ablated lithium atom reactions with H2 has been performed in solid para-hydrogen, normal hydrogen, neon, and argon. The LiH molecule and (LiH)(2,3,4) clusters were identified by IR spectra with isotopic substitution (HD, D(2), and H(2) + D(2)) and comparison to frequencies calculated by density functional theory and the MP2 method. The LiH diatomic molecule is highly polarized and associates additional H(2) to form primary (H(2))(2)LiH chemical complexes surrounded by a physical cage of solid hydrogen where the ortho and para spin states form three different primary complexes and play a role in the identification of the bis-dihydrogen complex and in characterization of the matrix cage. The highly ionic rhombic (LiH)(2) dimer, which is trapped in solid matrices, is calculated to be 22 kcal/mol more stable than the inverse hydrogen bonded linear LiH-LiH dimer, which is not observed here. The cyclic lithium hydride trimer and tetramer clusters were also observed. Although the spontaneous reaction of 2 Li and H(2) to form (LiH)(2) occurs on annealing in solid H(2), the formation of higher clusters requires visible irradiation. We observed the simplest possible chemical reduction of dihydrogen using two lithium valence electrons to form the rhombic (LiH)(2) dimer.     

Infrared spectra of matrix isolated and solid ethylene. Formation of ethylene dimers

Spectra of matrices with ethylene/argon ratios from 1/1 to 1/999 and a 1/24 ethylene/xenon matrix have been recorded in the temperature range 15–105 K. From relative i.r. intensities, frequency shifts and statistical calculations, the data are interpreted in terms of a monomer → dimer → aggregate → crystal scheme. It is proposed that the dimer, (C₂H₄)₂, has D_2d symmetry with a structure determined by quadruple hydrogen bonding and hydrogen-hydrogen repulsion. A method is described for calculation of the vibrational splitting due to interactions between the dimer molecular constituents.Solid ethylene has been studied between 15 and 85K. A transformation between two crystalline phases is characterized.     

The IR spectra of the products of the reaction of gallium atoms with iodine molecules in solid argon

The IR spectra of the reaction of gallium atoms with iodine molecules from the argon matrix are studied. Most of the bands observed have been assigned to stretching vibrations in tri-, di-, and monoiodide. Both the intensity relationship and the semiempirical estimates indicate that the valence angle should be no more than 110° in gallium di-iodide.