Kinetics of CO2 absorption by aqueous mixtures of N,N′-diethylethanolamine and polyamines

Aqueous solutions of N,Nʹ-diethylethanolamine (DEEA) are prospective high-capacity CO₂-capturing solvents. Their reactivity can be enhanced by promotion with absorption activators. Two polyamines were chosen as activators in this work, viz. (methylamino)propylamine (MAPA) and diethylene triamine (DETA). In a stirred cell reactor, kinetics of CO₂ absorption into aqueous DEEA/MAPA and DEEA/DETA mixtures was studied at 303 K. The molarity of DEEA was varied in the 2–2.5 M range, whereas the polyamine concentration was changed between 0.1 and 0.5 M. Pseudo–first-order rate constants were reported. Second-order rate constants for the CO₂ reactions with MAPA and DETA were determined too. DETA reacts faster than MAPA.     

Emission and transient absorption measurements of substitution effects of C–C triple bonds on relaxation processes of the fluorescent state of naphthalenes

Photophysical and photochemical properties of naphthalenes substituted with trimethylsilylethynyl, tert-butylethynyl, and trimethylsilylbutadiynyl groups were investigated by measurement of fluorescence yields, lifetimes, and triplet absorption. Introducing trimethylsilylethynyl and tert-butylethynyl groups to the 1-position of the naphthalene skeleton substantially enhanced fluorescence and intersystem crossing (ISC). The rates of fluorescence of 2-substituted naphthalenes were low. The effect of ethynyl groups on the 1-substituted naphthalenes was rationalized in terms of an increase of the transition moment along the short axis of the naphthalene skeleton. Substitution of the trimethylsilylbutadiynyl group at the 1 or 2-position of the naphthalene skeleton caused a considerable decrease in the fluorescence yield (approximately 0.01) and an increase in the ISC yield (0.99).     

Heat capacities and volumes of methanol+acetonitrile mixtures at 5 and 25°C

Densities and heat capacities of methanol + acetonitrile mixtures were determined over the whole composition range at 5 and 25°C. Apparent and partial molar volumes and heat capacities for both components of the mixture were calculated from these data. These functions for acetonitrile run monotonously over the whole composition range of the mixture at both temperatures, while those for methanol exhibit extrema (volumes-minimum and heat capacities-maximum) at high acetonitrile content. The reasons of the observed behavior of the system are discussed.     

Observation of ultrafast NH3 (Ã) state relaxation dynamics using a combination of time-resolved photoelectron spectroscopy and photoproduct detection

The ultrafast excited state relaxation of ammonia is investigated by resonantly exciting specific vibrational modes of the electronically excited NH(3) (?) state using three complementary femtosecond (fs) pump-probe techniques: time-resolved photoelectron, ion-yield and photofragment translational spectroscopy. Ammonia can be seen as a prototypical system for studying non-adiabatic dynamics and therefore offers a benchmark species for demonstrating the advantages of combining the aforementioned techniques to probe excited state dynamics, whilst simultaneously illuminating new aspects of ammonia's photochemistry. Time-resolved photoelectron spectroscopy (TRPES) provides direct spectroscopic evidence of σ* mediated relaxation of the NH(3) (?) state which manifests itself as coupling of the umbrella (ν(2)) and symmetric N-H stretch (ν(1)) modes in the photoelectron spectra. Time-resolved ion yield (TRIY) and time-resolved photofragment translation spectroscopy (TRPTS) grant a measure of the dissociation dynamics through analysis of the H and NH(2) photodissociation co-fragments. Initial vibrational level dependent TRIY measurements reveal photoproduct formation times of between 190 and 230 fs. Measurement of H-atom photoproduct kinetic energies enables investigation into the competition between adiabatic and non-adiabatic dissociation channels at the NH(3) (?)/NH(3) (X?) conical intersection and has shown that upon non-adiabatic dissociation into NH(2) (X?) + H, the NH(2) (X[combining tilde]) fragment is predominantly generated with significant fractions of internal vibrational energy.     

Intraconfigurational absorption spectroscopy of IrCl2−6 and IrBr2−6 in A2MX6-type host crystals

Near-IR absorption spectra for Ir⁴⁺ in A₂MX₆ (A  K, Rb, NH₄, M  Sn, Pt, Re, X  Cl, Br)-type hosts are discussed and compared to earlier work. Our data indicate that the effect of reduced host symmetry is quite small in this d⁵ system and that the IrCl²⁻₆ spectra can be interpreted in a manner paralleling previous studies on Ir⁴⁺ in cubic hosts. In some hosts, e.g., K₂PtCl₆, the IrBr²⁻₆ appears to have a vibronic pattern outside the experience with previous MX²⁻₆ results. Origin shifts and the nature of a vibronic progression were seen to correlate with host lattice counterion. By comparison to luminescence results of Flint and Paulusz, the latter data are proposed to be indicative of a strongly Jahn-Teller active e_g mode.     

Visible region absorption and excitation spectroscopy of K2ReCl6 and various ReCl2−6 containing A2MCl6 host crystals

For pure K₂ReCl₆ and ReCl²⁻₆ in K₂SnCl₆, K₂PtCl₆ and (NR₄)₂SnCl₆ (R = H, Et, Me, Pr) several new transitions located from 16000 to 20000 cm⁻¹ were found using absorption and excitation spectroscopy which cannot be assigned to intraconfigurational transitions of ReCl²⁻₆. These may be due to either impurity or site interaction effects or interconfigurational transitions. Everything possible has been done to rule out the former possibility and the host dependences are not consistent with site effects. If the latter source is correct, the appearance of these transitions indicates large deviations from the ligand field model in this sytem. In particular, exceptionally low values for the Dq parameter are required to fit the calculated ligand field energy levels to any interconfigurational assignment of the new transitions. This could be evidence of strong mixing of d-d and charge transfer states not represented in the ligand field model.     

Raman spectral studies on solutions of lithium bromide in binary mixtures of water and acetonitrile in the CH and CN stretching regions

Raman spectra of solutions of LiBr in mixtures of acetonitrile and water of varying compositions are reported. The symmetric CH stretching and CN stretching bands of acetonitrile are used as probes to study the ion molecular interactions. The full width at half maximum (FWHM) and frequency shifts of the bands under consideration are analysed. Vibrational correlation functions for the CH₃ stretching mode are computed and vibrational relaxation times are evaluated for additional information. The results are explained on the basis of ion-molecular interactions in general and preferential solvation of Br⁻ ions by water in particular.     

Intraconfigurational absorption spectroscopy of ReCl2−6 in various A2MCl6 host crystals

Low-temperature absorption and excitation spectra for Re⁴⁺ in distorted substitutional sites in K₂SnCl₆, [N(CH₃)₄]₂SnCl₆, [N(C₂H₅)₄]₂SnCl₆, [N(C₃H₇)₄]₂SnCl₆, and K₂SnBr₆ as well as in pure K₂ReCl₆ are discussed in comparison with the absorption spectra of Re⁴⁺ in cubic K₂PtCl₆, Cs₂ZrCl₆, and (NH₄)₂SnCl₆. Our data indicate that the effects of lowered symmetry are in general small and that the spectra can be interpreted in a manner paralleling earlier studies of Re⁴⁺ in cubic environments. Effects of reduced host symmetry appear to be smaller for this Kramers' ion than was previously noted for Os⁴⁺, a d⁴ system, but about equivalent to those noted for Ir⁴⁺, a d⁵ system, in the same host crystals. Origin shifts do not vary monotonically with cation size but do parallel results seen in Ir⁴⁺. In the N(C₂H₅)⁺₄ and N(C₃H₇)⁺₄ containing host crystals a significant splitting was found that correlated to two substitutional sites with parallel vibronic patterns. Low-symmetry splitting of U′_g states tended, on the contrary, to yield two sets of vibronic side bands with different intensity patterns which is an aid to assignment of the electronic state component.     

Failure of the linear mixture rule for the vibrational relaxation of C2H2Ar mixtures

Measurements of the vibrational relaxation time of mixtures of C₂H₂ and Ar were made behind shock waves in the temperature range 798–2645 K using a laser-beam deflection technique. The linear mixture rule, 1/pτ′ = Σ_iX_i/pτ′_i is found to fail, with deviations being most severe at high temperatures and far from equilbrium. Solution of the associated master equation confirms that this behaviour is theoretically expected.     

Experimental evaluation of electrical conductivity of ionanofluids based on water–[C2mim][CH3SO3] ionic liquids mixtures and alumina nanoparticles

Journal of Thermal Analysis and Calorimetry - Ionic liquids are one of the recent options for heat transfer enhancement due to their excellent features; nevertheless, their thermophysical and...     

Communication: Probing non-equilibrium vibrational relaxation pathways of highly excited C≡N stretching modes following ultrafast back-electron transfer

Fifth-order nonlinear visible-infrared spectroscopy is used to probe coherent and incoherent vibrational energy relaxation dynamics of highly excited vibrational modes indirectly populated via ultrafast photoinduced back-electron transfer in a trinuclear cyano-bridged mixed-valence complex. The flow of excess energy deposited into four C≡N stretching (ν(CN)) modes of the molecule is monitored by performing an IR pump-probe experiment as a function of the photochemical reaction (τ(vis)). Our results provide experimental evidence that the nuclear motions of the molecule are both coherently and incoherently coupled to the electronic charge transfer process. We observe that intramolecular vibrational relaxation dynamics among the highly excited ν(CN) modes change significantly en route to equilibrium. The experiment also measures a 7 cm(-1) shift in the frequency of a ～57 cm(-1) oscillation reflecting a modulation of the coupling between the probed high-frequency ν(CN) modes for τ(vis) < 500 fs.     

High-resolution Fourier transform infrared absorption spectroscopy of the ν6 band of c-C3H2

The gas-phase high-resolution absorption spectrum of the ν(6) band of cyclopropenylidene (c-C(3)H(2)) has been observed using a Fourier transform infrared spectrometer for the first time. The molecule has been produced by microwave discharge in an allene (3.3 Pa) and Ar (4.0 Pa) mixture inside a side arm glass tube. The observed spectrum shows a pattern of c-type ro-vibrational transitions in which the Q-branch lines strongly and distinctly stand out in the spectrum. A combined least-squares analysis of the observed 216 ro-vibrational transitions together with 28 millimeter-wave rotational transitions from the previous study has resulted in an accurate determination of the molecular constants in the ν(6) state. The band center is found to be at 776.11622(13) cm(-1) with one standard deviation in parentheses, which is 2.3% lower than the matrix isolation value. The intensity ratio I(3)(ν(3))/I(6)(ν(6)) obtained from the observed ν(3) and ν(6) bands, 1.90(9), is somewhat lower than the ratio estimated from ab initio (2.4-2.6) and DFT (2.8) calculations.     

Negative ion photoelectron spectroscopy of N2O− and (N2O)−2

We have recorded the photoelectron spectra of the gas phase negative ions N₂O⁻ and (N₂O)₂⁻ both of which were prepared in a nozzle ion source. The shift between the maxima of the two spectra is interpreted in terms of the dissociation energy of the dimer ion.     

[C4mim][PF6]和[C4mim][NTf2]离子液体辐射诱导的相行为及荧光行为变化

离子液体因其低挥发性, 高热稳定性及优良的萃取性能被认为是萃取分离放射性核素的新一代绿色溶剂, 而研究离子液体本身的辐射效应是其实际应用的重要前提. 本文以60Co为辐射源, 系统研究了γ辐照对两种常见的憎水性咪唑离子液体1-丁基-3-甲基咪唑六氟磷酸盐([C4mim][PF6])和1-丁基-3-甲基咪唑三氟甲基磺酰胺酸盐([C4mim][NTf2])的相行为及荧光行为的影响. 在相行为方面, γ辐照使离子液体的结晶驰豫时间增加, 导致其低温结晶延迟. 在荧光行为方面, γ辐照后离子液体的荧光光谱保持原有的“红边效应(red edge effect)”, 但随吸收剂量增加, 光谱整体发生红移(最大移动幅度达150 nm). 并且这种“红边效应”在辐照后离子液体的乙腈稀释剂中仍然存在, 且随稀释倍数增加光谱整体发生蓝移. [C4mim][PF6]和[C4mim][NTf2]离子液体辐照后的这种相行为及荧光行为的变化可归因于辐照对其阴阳离子空间相关性(缔合行为)的影响.     

气态二聚体[C1~6mim]2[BF4]2纳米微观结构的理论研究

在B3LYP/6-311+G(d,p)的水平上采用密度泛函理论研究了[C_nmim]+(n=1~6)与[BF_4]~ˉ形成二聚体[C_nmim]_2[BF_4]_2(n=1~6)的微观纳米结构。通过理论计算二聚体的相互作用能量发现,阴阳离子之间存在较强的氢键作用,且随着咪唑鎓烷基链的增加相互作用能也随之增加,另外,烷基侧链的长度会影响氢键强度。当咪唑鎓烷基侧链中C的个数大于4时,烷基尾部能够发生聚合,从而形成类胶束纳米结构。通过对自然布居分析、自然键轨道以及弱相互作用的分析和计算,同样证明了二聚体中存在较强的氢键作用,烷基侧链中碳的个数影响了离子液体的微观结构。     

Dynamics of photogenerated holes in nanocrystalline α-Fe2O3 electrodes for water oxidation probed by transient absorption spectroscopy

Transient absorption spectroscopy on the μs-s time scale is used to monitor the yield and decay dynamics of photogenerated holes in nanocrystalline hematite photoanodes. In the absence of a positive applied bias, these holes are observed to undergo rapid electron-hole recombination. The application of a positive bias results in the generation of long-lived (3 ± 1 s lifetime) photoholes.     

Synthesis and Stuctural Characterization of the Complex [Et4N]2[Ni（C2S

The heteroleptic dmit complex [Et4N]2[Ni2(C2S4)(C3S5)2] has been prepared by the reaction of NiCl2.H2O with Na2dmit, NaSC2H4OH in the MeOH solution. The compound has been characterized by X-ray diffraction study, IR and UV-Vis spectroscopy. Crystallographic data : space group: P21/n, a=11.843(2), b=11.079(1), c = 15.404(1)(), β=110.33(1)°, V = 1895.1()3, Z=2, Dc=1.62 g/cm3, μ=17.6 cm-1, F(000)=956, R=0.052, Rw=0.061. In the structure of the title complex, the tto (tto=tetrathioxalato) ligand in bridging form is chelated to two nickel atoms and dmit (dmit=1,3-dithiole-2-thione-4,5-dithiolate) ligands coordinated to nickel atoms.     

Quasiclassical Trajectory Study of Collisional Energy Transfer between Highly Excited C6F6 and N2 ,O2 and Ground State C6F6

Quasiclassical trajectory calculation (QCT) is used frequently for studying collisional energy transfer between highly vibrationally excited molecules and bath gases. In this paper, the QCT of the energy transfer between highly vibrationally excited C6F6 and N2 ,O2 and ground state C6F6 were performed. The results indicate that highly vibrationally excited C6F6 transferred vibrational energy to vibrational distribution of N2, O2 and ground state C6F6, so they are V-V energy transfer. Especially it is mainly V-V resonance energy transfer between excited C6F6 andground state C6F6, excited C6F6 transfers more vibrational energy to ground state C6F6 than to N2 and O2. The values of QCT, - (ΔEvib) of excited C6F6 are smaller than those of experiments.