Rotational spectrum of cyanoacetylene solvated with helium atoms

The high resolution microwave spectra of He(N)-HCCCN clusters were studied in the size ranges of 1-18 and 25-31. In the absence of an accompanying infrared study, rotational excitation energies were computed by the reptation quantum Monte Carlo method and used to facilitate the search and assignment of R(0) transitions from N > 6, as well as R(1) transitions with N > 1. The assignments in the range of 25-31 are accurate to +/-2 cluster size units, with an essentially certain relative ordering. The rotational transition frequencies decrease with N = 1-6 and then show oscillatory behavior for larger cluster sizes, which is now recognized to be a manifestation of the onset and microscopic evolution of superfluidity. For cluster sizes beyond completion of the first solvation shell the rotational frequencies increase significantly above the large-droplet limit. This behavior, common to other linear molecules whose interaction with He features a strong nearly equatorial minimum, is analyzed using path integral Monte Carlo simulations. The He density in the incipient second solvation shell is shown to open a new channel for long permutation cycles, thus increasing the decoupling of the quantum solvent from the rotation of the dopant molecule.     

High resolution infrared spectra of helium clusters seeded with isotopic carbon monoxide, HeN-13C 16O and HeN-12C 18O

Infrared spectra of isotopically substituted HeN-CO clusters (1 < N < 19) have been studied in order to extend the original results on the normal isotope. The same two series of R(0) transitions were observed, correlating with the a- and b-type transitions of He1-CO, with only small shifts in relative position. The previously obscured a-type line for He6-CO was detected. Examination of the small shifts among isotopomers showed remarkably smooth behavior, except in the "unstable" regions around N=7 (b-type series) and 15 (a-type series). The overall results firmly support the assignments and analysis given for the normal isotope.     

High resolution infrared spectroscopy of carbon dioxide clusters up to (CO2)13

Thirteen specific infrared bands in the 2350 cm(-1) region are assigned to carbon dioxide clusters, (CO(2))(N), with N = 6, 7, 9, 10, 11, 12 and 13. The spectra are observed in direct absorption using a tuneable infrared laser to probe a pulsed supersonic jet expansion of a dilute mixture of CO(2) in He carrier gas. Assignments are aided by cluster structure calculations made using two reliable CO(2) intermolecular potential functions. For (CO(2))(6), two highly symmetric isomers are observed, one with S(6) symmetry (probably the more stable form), and the other with S(4) symmetry. (CO(2))(13) is also symmetric (S(6)), but the remaining clusters are asymmetric tops with no symmetry elements. The observed rotational constants tend to be slightly (≈2%) smaller than those from the predicted structures. The bands have increasing vibrational blueshifts with increasing cluster size, similar to those predicted by the resonant dipole-dipole interaction model but significantly larger in magnitude.     

Rotational dynamics of solvated carbon dioxide studied by infrared, Raman, and time-resolved infrared spectroscopies and a molecular dynamics simulation

Rotational dynamics of solvated carbon dioxide (CO(2)) has been studied. The infrared absorption band of the antisymmetric stretch mode in acetonitrile is found to show a non-Lorentzian band shape, suggesting a non-exponential decay of the vibrational and/or rotational correlation functions. A combined method of a molecular dynamics (MD) simulation and a quantum chemical calculation well reproduces the observed band shape. The analysis suggests that the band broadening is almost purely rotational, while the contribution from the vibrational dephasing is negligibly small. The non-exponential rotational correlation decay can be explained by a simple rotor model simulation, which can treat large angle rotations of a relatively small molecule. A polarized Raman study of the symmetric stretch mode in acetonitrile gives a rotational bandwidth consistent with that obtained from the infrared analysis. A sub-picosecond time-resolved infrared absorption anisotropy measurement of the antisymmetric stretch mode in ethanol also gives a decay rate that is consistent with the observed rotational bandwidths.     

High resolution electronic absorption spectra of aniline, anilino and silicon dioxide

High resolution electronic absorption spectra of aniline and anilino free radical have been recorded in the vapor phase at room temperature by flash photolysis technique, and subsequent reactions have been investigated by kinetic spectroscopy. It was possible to follow the kinetics of the anilino radical's decay which occurred predominantly by bimolecular recombination. Decay parameters of anilino free radical were measured from the absorption bands.     

Rotational structure in the infrared spectra of carbon dioxide and nitrous oxide dimers

High-resolution infrared predissociation spectra have been measured for dilute mixtures of CO₂ and N₂O in helium. Rotational fine structure is clearly resolved for both (CO₂)₂ and (N₂O)₂, the linewidths being instrument-limited. This establishes that predissociation lifetimes are longer than approximately 50 ns.     

High resolution gas chromatographic determination of permanent gases with a helium ionization detector

The capability of the helium ionization detector (HID) to operate in connection with capillary columns for trace gas analyses has been evaluated. Two different capillary columns were considered: a PLOT fused silica column with molecular sleve and a thick film WCOT glass column with PS-255. The determination of trace impurities in gases can be achieved with evident advantages over classical adsorption columns, even using a split injection system. Direct on-column injections also have been investigated with promising results.     

Effects of carbon dioxide captured from ambient air on the infrared spectra of supported amines

Amino groups in highly dense coatings of amines on solid supports react with CO₂ of ambient air and form ammonium-carbamate ion pairs. These ion pairs change the properties of the amine-modified supports. In numerous studies, the corresponding infrared (IR) spectra have been misinterpreted. The presumption has been that such ion pairs would not form in ambient air, and therefore IR bands have been assigned to moieties of the support and the amines. Here, we discuss common misunderstandings of the IR spectra of amine-modified supports and highlight that proper sample handling is necessary before employing different characterization techniques. We exemplify by performing an IR spectroscopic study of a propylamine-modified porous silica. Such amine-modified supports are relevant to applications in gas separation, catalysis, controlled drug delivery and adsorption of pollutants from water.     

The interaction of metastable helium atoms with alkali atoms

Using crossed beams of ground state alkali atoms A (A = Li, Na, K, Rb, Cs) and metastable He(2³ S), He(2¹ S) atoms, we have measured the energy spectra of electrons resulting in the respective Penning ionization processes at: thermal collision energies. The data are interpreted to yield the well depthD _e ^* of the²Σ interaction potentials as follows: He(2³ S)+A:D _e ^* (A=Li)=868(20) meV;D _e ^* (Na)=740(25) meV;D _e ^* (K)=591(24) meV;D _e ^* (Rb)=546(18) meV;D _e ^* (Cs)=533(18) meV. He(2¹ S)+A:D _e ^* (Li)=330(17) meV;D _e ^* (Na)=277(24) meV;D _e ^* (K)=202(23) meV;D _e ^* (Rb)=219(18) meV;D _e ^* (Cs)=277(18) meV. The well depth for He(2³ S)+A(²Σ) is always close to 80% of the well depth for Li(2s)+A(X ¹Σ). The ionization cross sections for He(2¹ S)+A are about 3 to 4 times larger than those for He(2³ S)+A.     

Gas-phase spectra of the radiative recombination of nitrogen atoms at helium temperatures

The lowering of temperature from ≈ 300 K to ≈ 10 K caused drastic changes in the spectral composition of the recombinational afterglow of N atoms: the glow due to the B³Π_gν″ | A ³Σ⁺_uν″ transition with ν′ = 12-9 (λ ≈ 580 nm and λ ≈ 540 nm) disappeared whereas levels with ν′ = 8-5 (λ ≈ 560 nm) appeared. This effect is exlained in terms of Campbell and Thrush's recombination luminescence model (emitting B ³H_g state populated by radiationless transition from the lower A ³Σ⁺_u state of the N₂ molecule).     

Unraveling the absorption spectra of alkali metal atoms attached to helium nanodroplets

The absorption spectra of the first electronic exited state of alkali metal atoms on helium nanodroplets formed of both 4He and 3He isotopes were studied experimentally as well as theoretically. In the experimental part new data on the 2p<--2s transition of lithium on 3He nanodroplets are presented. The absorption spectrum changes drastically when compared to 4He droplets, in contrast to sodium where only marginal differences were observed in former studies. To explain these large differences and to answer some still open questions concerning the interaction of alkali metal atoms with helium nanodroplets, a model calculation was performed. New helium density profiles as well as a refined model allowed us to achieve good agreement with the experimental findings. For the first time the red-shifted intensities in the lithium and sodium spectra are explained in terms of enhanced binding configurations in the excited state displaced spatially from the ground state configurations.     

High resolution 1H NMR structural studies of sucrose octaacetate in supercritical carbon dioxide

High pressure (HP), high resolution (HR), proton nuclear magnetic resonance (1H NMR) spectroscopy has been utilized for the first time to investigate the solution structure of a carbohydrate based system, sucrose octaacetate (SOA), in supercritical CO2. The studies indicate that the average solution state conformation of the alpha-D-Glucopyranosyl ring of SOA in scCO2 medium is consistent with the 4C1 chair form, while the beta-D-fructofuranosyl ring adopts an envelope conformation. The investigations also suggest that scCO2 is a promising medium to study the solution structure and conformation of acetylated sugar systems. Spectral manifestations of a specific interaction between the acetate methyl protons and CO2 molecules are also presented.     

A high-resolution infrared spectroscopic investigation of the halogen atom-HCN entrance channel complexes solvated in superfluid helium droplets

Rotationally resolved infrared spectra are reported for the X-HCN (X = Cl, Br, I) binary complexes solvated in helium nanodroplets. These results are directly compared with those obtained previously for the corresponding X-HF complexes [J. M. Merritt, J. Küpper and R. E. Miller, Phys. Chem. Chem. Phys., 2005, 7, 67]. For bromine and iodine atoms complexed with HCN, two linear structures are observed and assigned to the (2)Sigma(1/2) and (2)Pi(3/2) ground electronic states of the nitrogen and hydrogen bound geometries, respectively. Experiments for HCN + chlorine atoms give rise to only a single band which is attributed to the nitrogen bound isomer. That the hydrogen bound isomer is not stabilized is rationalized in terms of a lowering of the isomerization barrier by spin-orbit coupling. Theoretical calculations with and without spin-orbit coupling have also been performed and are compared with our experimental results. The possibility of stabilizing high-energy structures containing multiple radicals is discussed, motivated by preliminary spectroscopic evidence for the di-radical Br-HCCCN-Br complex. Spectra for the corresponding molecular halogen HCN-X(2) complexes are also presented.     

High resolution infrared spectra of H2-Kr and D2-Kr van der Waals complexes

Infrared spectra of weakly bound hydrogen-krypton complexes have been studied at high spectral resolution (0.04 cm(-1)) using a long-path (154 m) low temperature (100 K) absorption cell and a Fourier transform spectrometer. In addition to spectra from the regions of the H(2) and D(2) fundamental vibrational bands in the midinfrared, the results also include the region of the pure rotational S(0)(0) transition of H(2) in the far infrared. A total of 219 measured line positions from these spectra have been fully assigned to specific quantum transitions and form the basis for determining a greatly improved semiempirical three-dimensional intermolecular potential energy surface for hydrogen-krypton in an accompanying paper.     

Modelling carbon dioxide molecule interacting with aquaglyceroporin and aquaporin-1 channels

Aquaporin (AQP) is a family of membrane proteins that enable water and small individual molecules to permeate cell membranes. Examples of these protein channels are aquaglyceroporin and aquaporin-1 (AQP1). Here, we investigate the permeability of carbon dioxide $(\hbox {CO}_2)$ ( CO 2 ) through both aquglyceroporin and AQP1 channels and explain their selectivity mechanisms. We provide a mathematical model which determines the molecular interaction potential between carbon dioxide molecule and an AQP channel. We evaluate this interaction using two approaches, namely discrete-continuum and completed discrete approaches. Both calculations agree well and our results indicate the acceptance of $(\hbox {CO}_2)$ ( CO 2 ) molecule into these channels which is in good agreement with other recent studies.     

Synergetic activation of carbon dioxide molecule using phenylazomethine dendrimers as a catalyst

Phenylazomethine dendrimers bearing a cobalt porphyrin core act as catalysts for CO₂ reduction in the presence of a strong Lewis acid such as lanthanide trifluoromethanesulfonate (Ln(OTf)₃). We investigated the catalytic activity using electrochemical measurements (cyclic voltammetry) on a glassy carbon electrode in a DMF solution. Dissolving CO₂ gas into the solution, the cyclic voltammograms displayed an irreversible increase of the cathodic current. This result suggests the catalytic reduction of CO₂. The redox potential (–1.3 V versus Fc/Fc⁺) at which the catalytic behavior was observed is 1.1 V higher than that catalyzed by cobalt tetraphenylporphyrin (CoTPP). The generation number (n) dependence of the dendrimer catalysts showed the maximum activity at n = 3. A significant decrease of the activity for the largest dendrimer (n = 4) indicates a steric effect, which prevents transmission of the substrate (CO₂ molecule) and electrons to the catalytic center (cobalt porphyrin core). For more efficient catalysis, a novel open-shell dendrimer having a pocket on one side of the molecule was designed and synthesized. Because the accessibility to the core in the opened shell improved, this dendrimer exhibited the highest catalytic activity. These results suggest that tuning of the local domain around the cobalt porphyrin center would lead to a decisive solution for further activation of the CO₂ molecule. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5229–5236, 2006     

High-resolution infrared spectroscopy of HCN-Agn (n = 1-4) complexes solvated in superfluid helium droplets

High-resolution infrared spectroscopy has been used to determine the structures, C-H stretching frequencies, and dipole moments of the HCN-Agn (n = 1-3) complexes formed in superfluid helium droplets. The HCN-Ag4 cluster was tentatively assigned based upon pick-up cell pressure dependencies and harmonic vibrational shift calculations. Ab initio and density functional theory calculations were used in conjunction with the high-resolution spectra to analyze the bonding nature of each cluster. All monoligated species reported here are bound through the nitrogen end of the HCN molecule. The HCN-Agn complexes are structurally similar to the previously reported HCN-Cun clusters, with the exception of the HCN-Ag binary complex. Although the interaction between the HCN and the Agn clusters follows the same trends as the HCN-Cun clusters, the more diffuse nature of the electrons surrounding the silver atoms results in a much weaker interaction.     

High resolution synchrotron X-ray investigation of carbon dioxide evolution in operating direct methanol fuel cells

The carbon dioxide evolution and bubble formation in an operating fuel has been studied by means of synchrotron X-ray radiography. Two different observation directions have been chosen: a through-plane insight has been employed to track the formation of bubbles starting at the corner of the lands of the flow field; a depth profile of the carbon dioxide evolution has been derived from cross sectional studies describing an affected area of up to 100 μm. The dynamics of the bubble formation and detachment of the bubbles from the position of formation is strongly correlated with the current density. Cracks and breaks in the catalyst layer which result from the preparation process are visible under operating conditions and a possible swelling of the catalyst layer does not reach a complete vanishing of the cracks.     

Reaction of hydrogen atoms with hydroxide ions to give solvated electrons

Exposure of aqueous alkaline glasses to ⁶⁰Co γ-rays followed by photobleaching to remove e_t⁻ resulted in E.S.R. spectra dominated by O_t^- and H·_t^-, but at ca. 110 K H·_t was lost and e_t⁻ reappeared.