Project description:The high-resolution infrared spectrum of isoprene has been observed under supersonic jet-cooled conditions in the region of the ν26 vibrational band near 992 cm-1. The spectrum was assigned and fit using a standard asymmetric top Hamiltonian, and an acceptable fit was obtained for transitions to excited state energy levels with J ≤ 6, with an error in the fit of 0.002 cm-1. For excited state energy levels with J > 6, a perturbation was present that prevented fitting using the standard asymmetric top Hamiltonian. Based on previous anharmonic frequency calculations and observed vibrational bands of isoprene, the perturbation is most likely caused by Coriolis coupling between the ν26 and ν17 vibrations or a combination band that lies near the ν26 band. The excited state rotational constants from the fit show reasonable agreement with previous anharmonic calculations performed at the MP2/cc-pVTZ level of theory. The jet-cooled spectrum is compared with previous high-resolution measurements of this band at room temperature and shows that understanding the perturbation will be necessary to accurately model this vibrational band.
Project description:Infrared spectroscopic study of neutral water clusters is crucial to understanding of the hydrogen-bonding networks in liquid water and ice. Here we report infrared spectra of size-selected neutral water clusters, (H2O) n (n = 3-6), in the OH stretching vibration region, based on threshold photoionization using a tunable vacuum ultraviolet free-electron laser. Distinct OH stretch vibrational fundamentals observed in the 3,500-3,600-cm-1 region of (H2O)5 provide unique spectral signatures for the formation of a noncyclic pentamer, which coexists with the global-minimum cyclic structure previously identified in the gas phase. The main features of infrared spectra of the pentamer and hexamer, (H2O) n (n = 5 and 6), span the entire OH stretching band of liquid water, suggesting that they start to exhibit the richness and diversity of hydrogen-bonding networks in bulk water.
Project description:The low energy structures of neutral and cationic pyrene clusters containing up to seven molecules are searched through a global exploration scheme combining parallel tempering Monte Carlo algorithm and local quenches. The potential energies are computed at the density functional based tight binding level for neutrals and configuration interaction density functional based tight binding for cations in order to treat properly the charge resonance. New simplified versions of these schemes are also presented and used during the global exploration. Neutral clusters are shown to be made of compact assemblies of sub-blocs containing up to three units whereas cations present a charged dimer or trimer core surrounded by neutral units. The structural features of the clusters are analyzed and correlated for the cation with the charge distribution. The stability of clusters is also discussed in terms of cohesive and evaporation energies. Adiabatic and vertical ionization potentials are also discussed.
Project description:During champagne cork popping, the CO2/H2O gas mixture initially under pressure in the bottleneck freely expands into ambient air and experiences adiabatic cooling. A comparison between the condensation phenomena accompanying cork popping from bottles stored at 20° and 30°C was made. The initial headspace-to-ambient-pressure ratio much exceeded the critical ratio needed for the gas mixture to reach Mach 1, thus forming under-expanded supersonic CO2 freezing jets expelled from the throat of the bottlenecks. It was emphasized that, after adiabatic cooling and with a saturation ratio for gas-phase CO2 about twice higher for the bottles stored at 30°C, dry ice CO2 clusters grow bigger and reach the critical size needed to achieve the Mie scattering of light. Moreover, during the very first millisecond following cork popping, evanescent normal shock waves (or Mach disks) were unveiled in the jets, until the reservoir-to-ambient-pressure ratio goes below a critical ratio.
Project description:We report the first helium-tagged electronic spectra of cationic adamantane clusters, along with its singly, doubly, and triply dehydrogenated analogues embedded in helium droplets. Absorption spectra were measured by recording the evaporation of helium atoms as a function of laser wavelength in the range of 300-2150 nm. Experimental spectra are coupled with simulated spectra obtained from quantum chemical calculations. The spectrum of cationic adamantane agrees with the electronic photodissociation spectrum measured previously, with an additional low-energy absorption at around 1000 nm. The spectra of the dehydrogenated molecules present broad absorptions exclusively in the high-energy region (300-600 nm). For the higher order adamantane dimer and trimer ions, strong absorptions are observed in the low-energy region (900-2150 nm), rationalised by transitions delocalised over two adamantane units.
Project description:We present the analysis of formaldehyde (HCHO) in anhydrous methanol (CH3OH) as a case study to quantify HCHO in non-aqueous samples. At higher concentrations (C > 0.07 M), we detect a product of HCHO, methoxy methanol (MM, CH3OCH2OH), by Fourier transform infrared spectroscopy, FTIR. Formaldehyde reacts with CH3OH, CD3OH, and CD3OD as shown by FTIR with a characteristic spectral feature around 1,195 cm-1 for CH3OH used for the qualitative detection of MM, a formaldehyde derivative in neat methanol. Ab initio calculations support this assignment. The extinction coefficient for 1,195 cm-1 is in the order of 1.4 × 102 M-1cm-1, which makes the detection limit by FTIR in the order of 0.07 M. For lower concentrations, we performed the quantitative analysis of non-aqueous samples by derivatization with dinitrophenylhydrazine (DNPH). The derivatization uses an aqueous H2SO4 solution to yield the formaldehyde derivatized hydrazone. Ba(OH)2 removes sulfate ions from the derivatized samples and a final extraction with isobutyl acetate to yield a 1:1 methanol: isobutyl acetate solvent for injection for electrospray ionization (ESI). The ESI analysis gave a linear calibration curve for concentrations from 10 to 200 µM with a time-of-flight analyzer (TOF). The detection and quantification limits are 7.8 and 26 μM, respectively, for a linear correlation with R 2 > 0.99. We propose that the formaldehyde in CH3OH is in equilibrium with the MM species, without evidence of HCHO in solution. In the presence of water, the peaks for MM become less resolved, as expected from the well-known equilibria of HCHO that favors the formation of methylene glycol and polymeric species. Our results show that HCHO, in methanol does not exist in the aldehyde form as the main chemical species. Still, HCHO is in equilibrium between the production of MM and the formation of hydrated species in the presence of water. We demonstrate the ESI-MS analysis of HCHO from a non-aqueous TiO2 suspension in methanol. Detection of HCHO after illumination of the colloid indicates that methanol photooxidation yields formaldehyde in equilibrium with the solvent.
Project description:Unraveling methanol's infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration. These experiments are accompanied by calculating wavenumbers involving anharmonicity and mode-coupling based on the vibrational configuration interaction approach. This allows for an unambiguous assignment of all fundamentals and resonances in the mid-infrared spectrum. An increasing degree of deuteration lifts resonances and aids in assigning bands uniquely. It also becomes evident that different notations typically used in chemistry or physics to describe molecular vibration from spectroscopy fail to describe the spectra appropriately. We highlight the shortcomings and suggest a more elaborate analysis using Sankey diagrams to unambiguously identify spectral features. Consequently, we demystify debated resonances occurring from various stretches and deformations of the methyl group.
Project description:The cationic fragmentation products in the dissociative ionization of pyridine and benzonitrile have been studied by infrared action spectroscopy in a cryogenic ion trap instrument at the Free-Electron Lasers for Infrared eXperiments (FELIX) Laboratory. A comparison of the experimental vibrational fingerprints of the dominant cationic fragments with those from quantum chemical calculations revealed a diversity of molecular fragment structures. The loss of HCN/HNC is shown to be the major fragmentation channel for both pyridine and benzonitrile. Using the determined structures of the cationic fragments, potential energy surfaces have been calculated to elucidate the nature of the neutral fragment partner. In the fragmentation chemistry of pyridine, multiple non-cyclic structures are formed, whereas the fragmentation of benzonitrile dominantly leads to the formation of cyclic structures. Among the fragments are linear cyano-(di)acetylene˙+, methylene-cyclopropene˙+ and o- and m-benzyne˙+ structures, the latter possible building blocks in interstellar polycyclic aromatic hydrocarbon (PAH) formation chemistry. Molecular dynamics simulations using density functional based tight binding (MD/DFTB) were performed and used to benchmark and elucidate the different fragmentation pathways based on the experimentally determined structures. The implications of the difference in fragments observed for pyridine and benzonitrile are discussed in an astrochemical context.
Project description:Astrophysical flows exhibit rich behaviour resulting from the interplay of different forms of energy-gravitational, thermal, magnetic and radiative. For magnetic cataclysmic variable stars, material from a late, main sequence star is pulled onto a highly magnetized (B>10 MG) white dwarf. The magnetic field is sufficiently large to direct the flow as an accretion column onto the poles of the white dwarf, a star subclass known as AM Herculis. A stationary radiative shock is expected to form 100-1,000 km above the surface of the white dwarf, far too small to be resolved with current telescopes. Here we report the results of a laboratory experiment showing the evolution of a reverse shock when both ionization and radiative losses are important. We find that the stand-off position of the shock agrees with radiation hydrodynamic simulations and is consistent, when scaled to AM Herculis star systems, with theoretical predictions.
Project description:Benzo[a]pyrene (B[a]P), polychlorinated biphenyls (PCBs), and polybrominated diphenyl ethers (PBDEs) are persistent contaminants and concern has arisen over co-exposure of organisms when the chemicals exist in mixtures. Herein, attenuated total reflection Fourier transform infrared spectroscopy was used to identify biochemical alterations induced in cells by single and binary mixtures of these environmental chemicals. It was also investigated as a method to identify if interactions are occurring in mixtures and as a possible tool to predict mixture effects. Mallard fibroblasts were treated with single and binary mixtures of B[a]P, PCB126, PCB153, BDE47, and BDE209. Comparison of observed spectra from cells treated with binary mixtures with expected additive spectra, which were created from individual exposure spectra, indicated that in many areas of the spectrum, less-than-additive binary mixture effects may occur. However, possible greater-than-additive alterations were identified in the 1650-1750 cm-1 lipid region and may demonstrate a common mechanism of B[a]P and PCBs or PBDEs, which can enhance toxicity in mixtures.