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31.
Mª Ángeles Fernández de la OssaMaría López-López Mercedes TorreCarmen García-Ruiz 《Trends in analytical chemistry : TRAC》2011,30(11):1740-1755
This work presents an updated overview of the analytical techniques used to study highly-nitrated nitrocellulose, which is used in explosives and is of forensic interest. Most articles published in the past decade were designed:(1) to investigate polymeric parameters of nitrocellulose (e.g., molar mass distribution, viscosity and specific refractive index) by size-exclusion chromatography;(2) to determine the morphological and thermal characteristics of nitrocellulose using thermal and spectroscopic techniques; and,(3) to study the thermal, biological and mechanical degradation of nitrocellulose by thermal, spectroscopic, and mass spectrometric (MS) techniques, alone or coupled to gas chromatography.However, the few papers that focused on the determination of nitrocellulose used in explosives employed analytical techniques [e.g., vibrational techniques (infrared and Raman spectroscopy), MS and ion-mobility spectrometry (IMS) and liquid chromatography (LC) (high-performance LC and ion chromatography)]. Most of the information reported by these techniques has been qualitative. Only quantitative determination of nitrocellulose or its nitrogen content has been performed by measuring the nitrite and/or nitrate ions released from its basic hydrolysis. 相似文献
32.
M. E. Castro C. Muñoz‐Caro A. Niño 《International journal of quantum chemistry》2011,111(14):3681-3694
This work presents a structural and vibrational theoretical study of n‐propyl cyanide as a function of the nitrile and methyl torsional modes. A potential energy hypersurface is built at the MP4(SDQ)/aug‐cc‐pVTZ//MP2/aug‐cc‐pVTZ theory level. The equilibrium structure is found in a gauche conformation. Another minimum is found for the trans form. The maximum appears in a cis conformation. For the first time, the interconversion barriers between the different forms are calculated. A two‐dimensional anharmonic vibrational Hamiltonian is built for the nitrile and methyl torsional modes. We find the vibrational energy levels to organize in two stacks associated to the gauche and trans forms. Fundamental frequencies of 113.12 and 220.54 cm?1 are predicted for the nitrile and methyl torsions in the equilibrium, gauche, conformer. In addition, we find symmetry allowed transitions between the gauche and trans energy levels stacks. The lowest transition is predicted to appear at 24.49 cm?1. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2011 相似文献
33.
Dimethyl-2-(5-acetyl-2,2-dimethyl-4,6-dioxo-1,3-dioxan-5-yl)-3-(triphenylphosphinylidene)succinate has been synthesized and characterized by elemental analysis, FT-IR and 1H, 13C and 31P NMR. The vibrational wavenumbers, gauge including atomic orbital (GIAO) 1H and 13C chemical shift values of title compound in the ground state have been computed with density functional theory method (DFT) and the B3LYP functional. The basis sets used are 6-311G(d,p) and 6-31G(d). The harmonic vibrational wavenumbers have been computed and the scaled values have been compared with the experimental FT-IR spectra. The complete assignments have been performed on basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method. Most of the computed wavenumbers are found to be in good agreement with the observed spectrum. 相似文献
34.
Nirmal Kumar Sarkar Joydeep ChoudhurySrinivasa Rao Karumuri Ramendu Bhattacharjee 《Vibrational Spectroscopy》2011,56(1):99-104
Using the U(4) algebraic model, in this work we report a study of the vibrational spectra of SO2, H2018 and D2O16. The inclusion of intermode couplings in algebraic models has been stated to give a deep insight into detailed spectroscopy for these bent XY2 molecules. Improved set of algebraic parameters has been reported to provide improved RMS deviations for these molecules. 相似文献
35.
Katarzyna HeliosRafa? Wysokiński Adam PietraszkoDanuta Michalska 《Vibrational Spectroscopy》2011,55(2):207-215
The crystal and molecular structure of a polymeric Cu(II)-orotate complex, [Cu(μ-HOr)(H2O)2]n, has been reinvestigated by single crystal X-ray diffraction. It is shown that several synergistic interactions: two axial Cu-O interactions; intramolecular and intermolecular hydrogen bonds; and π-π stacking between the uracil rings contribute to the stability of the crystal structure. The Raman and FT-IR spectra of the title complex are reported for the first time. Comprehensive theoretical studies have been performed by using three unrestricted DFT methods: B3LYP; and the recently developed M06, and M05-2X density functionals. Clear-cut assignments of all the bands in the vibrational spectra have been made on the basis of the calculated potential energy distribution, PED. The very strong Raman band at 1219 cm−1 is diagnostic for the N1-deprotonation of the uracil ring and formation of the copper-nitrogen bond, in this complex. The Cu-O (carboxylate) stretching vibration is observed at 287 cm−1 in the IR spectrum, while the Cu-N (U ring) stretching vibration is assigned to the strong Raman band at 263 cm−1. The molecular structure and vibrational spectra (frequencies and intensities) calculated by the M06 functional method are very similar to the results obtained by the B3LYP method, but M06 performs better than B3LYP in calculations of the geometrical parameters and vibrational frequencies of the interligand O-H?O hydrogen bonding. Unfortunately, the M05-2X method seriously overestimates the strength of interligand hydrogen bond. 相似文献
36.
James R. Durig Savitha S. Panikar Keith A. GlennYa Ying Zheng Gamil A. Guirgis 《Vibrational Spectroscopy》2011,55(2):250-257
Infrared and Raman spectra (3500-60 cm−1) of gas and/or liquid and solid 1-chloro-1-silacyclopentane (c-C4H8SiClH) have been recorded and the vibrational data indicate the presence of a single conformer with no symmetry which is consistent with the twisted form. Ab initio calculations with a variety of basis sets up to MP2(full)/aug-cc-pVTZ predict the envelope-axial and envelope-equatorial conformers are saddle points with nearly the same energies but much lower in energy than the planar conformer. Density functional theory calculations by the B3LYP method predicts slightly lower energies for the two envelope forms and considerably lower for the planar form. By utilizing the MP2(full)/6-31G(d) calculations the force constants, frequencies, infrared intensities, band contours, Raman activities, and depolarization values have been obtained to support the vibrational assignment. Estimated r0 structural parameters have been obtained from adjusted MP2(full)/6-311 + G(d, p) calculations. These experimental and theoretical results are compared to the corresponding quantities of some other five-membered rings. 相似文献
37.
Fumaric acid was reacted with the binary superacidic systems HF/SbF5 and HF/AsF5. The O,O'-diprotonated [C4H6O4]2+([MF6]–)2 (M = As, Sb) and the O-monoprotonated [C4H5O4]+[MF6]– (M = As, Sb) species are formed depending on the stoichiometric ratio of the Lewis acid to fumaric acid. The colorless salts were characterized by low-temperature vibrational spectroscopy. In case of the hexafluoridoantimonates single-crystal X-ray structure analyses were carried out. The [C4H6O4]2+([SbF6]–)2 crystallizes in the monoclinic space group C2/c with four formula units per unit cell and [C4H5O4]+[SbF6]– crystallizes in the triclinic space group P1 with one formula unit per unit cell. The protonation of fumaric acid does not cause a notable change of the C=C bond length. The experimental data are discussed together with quantum chemical calculations of the cations [C4H6O4 · 4 HF]2+ and [C4H6O4 · 2 H2CO · 2 HF]2+. 相似文献
38.
Very accurate vibrational spectra of silicates are obtained from DFT calculations if the appropriate Hamiltonian is used. Theoretical considerations suggest that the Hartree-Fock component of ACM1 hybrid functionals should be 1/6 instead of 1/4 for this class of compounds. When applied to the PBE functional this removes the scaling error of the calculated vibrational frequencies. Calculations using this PBE(n = 6) functional in combination with optimized Gaussian basis sets result in very small remaining deviations between observed and calculated Raman shifts, with standard uncertainties of ≈3.5 cm−1, maximum deviations of ≈10 cm−1, and no significant systematic trends. This has been confirmed for a wide range of silicate structures, for which high-quality Raman spectra have been published: forsterite α-Mg2SiO4 (nesosilicate), γ-Y2Si2O7 (sorosilicate), K2Ca3Si3O10 (oligosilicate), K2Ca4Si8O21 (phyllosilicate), and α-quartz SiO2 (tectosilictae). 相似文献
39.
In view of existing contradictory assignments of the symmetrical stretching vibrations associated with the formal C-C and C-F bonds of trans/cis oxalyl fluoride, an additional theoretical analysis of the corresponding calculated wavenumbers was preformed on trans-C2O2F2 and cis-C2O2F2 based on previously calculated ab initio scaled force fields at the HF/6-31G computational level and new force fields calculated at the MP2/aug-cc-pVTZ level. This novel analysis included computational data from the isotopic shifts brought about by incorporating 13C and 14C atoms into the structure. A detailed examination of the calculated wavenumbers made it possible to validate the assignments of the ν2 and ν3 wavenumbers in the trans-C2O2F2 and cis-C2O2F2 molecules as the formal C-C bond stretching and the formal C-F bond symmetrical stretching vibrations, respectively. 相似文献
40.