Calculation of conformations and vibrational spectra of a fragment of the 2,6-hydroxyethyl cellulose molecule

We have used the molecular mechanics method for conformational analysis of a fragment of the molecule of a water-soluble cellulose ether: 2,6-hydroxyethyl cellulose (2,6-HEC). As a result of rotation about the C-C and C-O bonds within the bulky side substituents on the C5 and C2 backbone atoms in the fragment of the 2,6-HEC molecule, we have obtained 12 of the most stable conformers for this fragment with strain energies differing within the range 0–2.3 kcal/mol. We have shown that the most stable conformers have the following conformations for the groups of atoms on the bonds C5-C6, C6-O6, C13-O6, C10-C13: gt, g⁻, g⁺, g⁺ and gg, t, g⁺, g⁺ respectively; and on the bonds C2-O2, C11-O2, C7-C11: g⁺g⁻, g⁻, g⁺ respectively. For the conformers obtained, using the same method we calculated the frequencies and the potential energy distribution (PED) for their normal vibrations (NV). Comparative analysis showed high sensitivity of both the frequency and the PED of the normal vibrations to conformational changes within the indicated bulky substituents over the entire analyzed spectral region (800–1500 cm⁻¹ for the methylene groups). We introduce the concept of “conformational characteristicity” of both the frequency and the mode of vibration. We show that it is possible to analyze the conformations of the bulky substituents of the fragment of the 2,6-HEC molecule using its vibrational spectrum. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 42–53, January–February, 2006.     

A study of the molecular structure of DL-serine with the method of low-temperature IR spectroscopy

Use of low-temperature IR spectroscopy in studies of compounds with a developed system of hydrogen bonds such as DL-serine revealed a complete set of vibrational frequencies. The region of manifestation of stretching vibrations of OH groups involved in the formation of strong hydrogen bonds was found. It is shown experimentally that in a crystal some of the molecules of SL-serine exist in the nonionized form. On the basis of analysis of experimental data, frequency ranges of stretching deformation and torsional vibrations of NH ₃ ⁺ , COO⁻, and OH groups were determined more accurately. It is found that in the crystals there exist molecules of DL-serine with different spatial orientation of NH ₃ ⁺ COO⁻, and COH groups. It is shown that conformational diversity of molecular structures is also preserved at T=18 K. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 6, pp. 864–868, November–December, 1998.     

Conformational analysis of 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinone derivatives by the density functional method and IR spectroscopy

We have used the PBE/3z, B3LYP/6-31G, B3LYP/6-31G(d), and B3LYP/6-311G(d) methods to study the conformational mobility of 2,3-dihydro-3-O-(1,4-naphthoquinon-2-yl)-2-oxo-1,4-naphthoquinones (1–4). We have shown that more than 99% of these compounds exist as the major tautomeric form, while differences in the structure of the Q_2H (2,3-dihydro-2-oxo-1,4-naphthoquinones) and Q_1,4 (1,4-naphthoquinon-2-yl) moieties lead to qualitative differences in the internal rotation potentials of the ethyl substituents V(θ_Et−1) and V(θ_Et−2), and consequently each of compounds 1−4 exists as six different rotameric forms. For diquinone 3, we have calculated the dependences of the frequencies (ν) and intensities (A) of the normal vibrations on the torsional angles θ_Et−1 and θ_Et−2, and also on the changes in the geometry of the ether bond. We have found that the values of ν and A for the bands in the carbonyl region of the IR spectrum change little on going from one rotameric form to another, and also for the in-plane bends of the ether bond, and change considerably for the out-of-plane bends of the ether bond. However, for T ≤ 300 K, there is no qualitative change in the overall contour, and it can be interpreted based on a simple additive model. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 573–581, September–October, 2006.     

Fluorescence excitation spectra of jet-cooled carbazole complexes with monohydric alcohols

We have analyzed the fluorescence excitation spectra of carbazole complexes with a single molecule of methyl, deuterated methyl, ethyl, and propyl (1-propanol and 2-propanol) alcohols, cooled in a supersonic jet. We have determined the shifts in the fluorescence excitation spectra of the complexes relative to the frequency of the purely electronic transition of unbound carbazole. They occur as a result of formation of hydrogen bonds between the N-H group of the carbazole and the OH group of the alcohols. The frequencies of stretching vibrations of the hydrogen bonds with different alcohols vary within the range 150–157 cm⁻¹, while the frequencies of the bending vibrations vary in the range 21–22.9 cm⁻¹. From the shape of the rotational contours of the bands for the purely electronic and vibronic transitions of the complexes, we determined that they belonged to rotational conformers. We calculated the equilibrium configurations of the complexes in the ground state. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 6, pp. 756–760, November–December, 2007.     

Influence of carbon additive on the properties of spherical Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript> and LiFePO<Subscript>4</Subscript> materials for lithium-ion batteries

Preparing spherical particles with carbon additive is considered as one effective way to improve both high rate performance and tap density of Li₄Ti₅O₁₂ and LiFePO₄ materials. Spherical Li₄Ti₅O₁₂/C and LiFePO₄/C composites are prepared by spray-drying–solid-state reaction method and controlled crystallization–carbothermal reduction method, respectively. The X-ray diffraction characterization, scanning electron microscope, Brunauer–Emmett–Teller, alternating current impedance analyzing, tap density testing, and electrochemical property measurements are investigated. After hybridizing carbon with a proper quantity, the crystal grain size of active materials is remarkably decreased and the electrochemical properties are obviously improved. The Li₄Ti₅O₁₂/C and LiFePO₄/C composites prepared in this work are spherical. The tap density and the specific surface area are as high as 1.71 g cm⁻³ and 8.26 m² g⁻¹ for spherical Li₄Ti₅O₁₂/C, which are 1.35 g cm⁻³ and 18.86 m² g⁻¹ for spherical LiFePO₄/C powders. Between 1.0 and 3.0 V versus Li, the reversible specific capacity of the Li₄Ti₅O₁₂/C is more than 150 mAh g⁻¹ at 1.0-C rate. Between 2.5 and 4.2 V versus Li, the reversible capacity of the LiFePO₄/C is close to 140 mAh g⁻¹ at 1.0-C rate.     

(T1u+T1g)⊗(hg+τ1u)vibronic interaction and superconductivity in C 60 n− fullerides

The closeness of low-lying T_1u and T_1g levels of C ₆₀ ⁻ could enable their mixing under an odd parity vibration of (T_{1 u} + T_{1 g} ⊗ (h_g + τ_{1 u})type. In addition, the two levels are susceptible to Jahn-Teller interaction due to five-fold degenerate h_g vibrations. This complex problem of (T_1u+T_1g)⊗(h_g+τ_1u) vibronic interaction is transformed to a form similar to T_2g ⊗ (ε_g + τ_2g) vibronic problem of octahedral symmetry. The problem is analysed in an infinite coupling model and compared with the experimental spectroscopic results for the C ₆₀ ⁻ radical. The resulting parameters are used to calculate the pair-binding energy and superconducting transition temperature in C ₆₀ ⁿ⁻ fullerides. Vibronic mixing with the T_1g level is found to be responsible for maximising the pair-binding energy at the doping level n=3. It is also found to be an important source of T_c enhancement.     

IR Spectroscopic Investigation and Conformational Analysis of Unsaturated C<Superscript>20</Superscript> and C<Superscript>22</Superscript> Steroid Alcohols

With the IR-spectroscopy method and the quantum-chemical AM1 method, the Δ²² and Δ²³ steroids containing a hydroxyl group at C²⁰ or C²² have been studied in order to elucidate the mutual arrangement in space of the hydroxyl group and of the double bond in the side chain of the molecules. The conformational analysis of steroid alcohols has been performed and the population of their stable conformers has been calculated. The frequencies of the bands in the IR spectra of alcohols in the region of the stretching vibration of OH groups have been assigned to certain conformers and the possibility of formation of the intramolecular hydrogen bond of the OH groups with the π-electron cloud of C=C bonds has been analyzed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 317–324, May–June, 2005.     

Four quasi-particle level at 2256 keV in182Re

In-beam nuclear spectroscopic studies of¹⁸²Re, following the reaction¹⁸¹Ta(α, 3n)¹⁸²Re have been made using gamma-ray and internal conversion electron techniques.K-conversion coefficients for several transitions have been measured and the multi-polarities of the various transitions assigned. In particular, the spin and parity of the four-quasi-particle isomeric level at 2256 keV were determined to be 16⁻. Theg-factor of this level has been measured to beg = 0·32 ± 0·05. On the basis of theg-factor and the decay pattern of this level, a configuration {v9/2⁺ [624↑]v7/2⁻ [514↓]v7/2⁻ [503↑]π9/2⁻ [514↑]} _k ^x = 16⁻ has been assigned to this level. The nature of the retardation of the gamma transitions deexciting this level is discussed. It is argued that the measured retardation factors can be explained if the nucleus has a triaxial shape.     

Weak e+e− lines from internal pair conversion observed in collisions of 238U with heavy nuclei

We present the results of a Doppler-shift correction to the measured e⁺e⁻–sum-energy spectra obtained from e⁺e⁻–coincidence measurements in ²³⁸U +²⁰⁶Pb and ²³⁸U +¹⁸¹Ta collisions at beam energies close to the Coulomb barrier, using an improved experimental setup at the double-Orange spectrometer of GSI. Internal-Pair-Conversion (IPC) e⁺e⁻ pairs from discrete nuclear transitions of a moving emitter have been observed following Coulomb excitation of the 1.844 MeV (E1) transition in ²⁰⁶Pb and neutron transfer to the 1.770 MeV (M1) transition in ²⁰⁷Pb. In the collision system ²³⁸U +¹⁸¹Ta, IPC transitions were observed from the Ta-like as well as from the U-like nuclei. In all systems the Doppler-shift corrected e⁺e⁻–sum-energy spectra show weak lines at the energies expected from the corresponding γ–ray spectra with cross sections being consistent with the measured excitation cross sections of the γ lines and the theoretically predicted IPC coefficients. No other than IPC e⁺e⁻–sum-energy lines were found in the measured spectra. The transfer cross sections show a strong dependence on the distance of closest approach (R_min), thus signaling also a strong dependence on the bombarding energy close to the Coulomb barrier. Received: 22 July 1997 / Revised version: 15 October 1997     

Electron-vibrational energy exchange in collisions of Ar atoms in the 3P2 metastable state with N2(X1S g+ ) molecules

Rate constants for electron-vibrational energy exchange Ar(³ P ₂) + N₂(X ¹Σ _g ⁺, ν = 0) → Ar(¹ S ₀) + N₂(C ³Π _u , ν′), where ν′ = 0, 1, 2, were calculated. Calculations were performed taking into account the presence of a resonance in electron scattering by N₂(X ¹Σ _g ⁺). As a result, the interaction of Ar(³ P ₂) with N₂(X ¹Σ _g ⁺, ν = 0) was characterized by attraction and, in the end, intersection of electron-vibrational potential surfaces correlating with Ar(³ P ₂) + N₂(X ¹Σ _g ⁺, ν = 0) and Ar(¹ S ₀) + N₂(C ³Π _u , ν′) at interparticle distances of 2.5–3.5 ?. Exchange interaction at which electron-vibrational transitions in the region of intersection of electron-vibrational transitions in the region of intersection of electron-vibrational potential surfaces accompanied by spin exchange were induced was calculated by the asymptotic method. The rate constants determined at 300–600 K were on the order of 10⁻¹¹−10⁻¹² cm³/s and weakly increased as the temperature grew. Mainly the C ³Π _u , ν′ = 0 state of the N₂ molecule was populated. The calculation results were in satisfactory agreement with the experimental data obtained at 300 K.