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The heterogeneous oxidation reaction of single aqueous ascorbic acid (AH$_2$) aerosol particles with gas-phase ozone was investigated in this study utilizing aerosol optical tweezers with Raman spectroscopy. The measured liquid-phase bimolecular rate coefficients of the AH$_2$ + O$_3$ reaction exhibit a significant pH dependence, and the corresponding values at ionic strength 0.2 M are $(3.1 \pm 2.0) \times 10^5$ M$^{-1}$s$^{-1}$ and $(1.2 \pm 0.6) \times 10^7$ M$^{-1}$s$^{-1}$ for pH $\approx$ 2 and 6, respectively. These results measured in micron-sized droplets agree with those from previous bulk measurements, indicating that the observed aerosol reaction kinetics can be solely explained by liquid phase diffusion and AH$_2$ + O$_3$ reaction. Furthermore, the results indicate that high ionic strengths could enhance the liquid-phase rate coefficients of the AH$_2$ + O$_3$ reaction. The results also exhibit a negative ozone pressure dependence that can be rationalized in terms of a Langmuir-Hinshelwood type mechanism for the heterogeneous oxidation of AH$_2$ aerosol particles by gas-phase ozone. The results of the present work imply that in acidified airway-lining fluids the antioxidant ability of AH$_2$ against atmospheric ozone will be significantly suppressed.

The kinetics of CH$_2$OO reaction with ozone has been studied by monitoring CH$_2$OO with time-resolved infrared (IR) absorption spectroscopy, which utilized fast chirped IR pulse train from a quantum cascade laser [J. Chem. Phys. 146, 244302 (2017)]. CH$_2$OO was prepared by photolyzing a gas mixture of CH$_2$I$_2$/O$_2$/O$_3$ at 352 nm; the photolysis wavelength was chosen to minimize the photodissociation of O$_3$. The measured rate coefficient at 298 K and 30 Torr is (6.7$\pm$0.5)x10$^{-14}$ cm$^3$sec$^{-1}$, independent of pressure from 30 to 100 Torr. The result indicates that previous ab initio calculations either underestimated or overestimated this reaction rate by one order of magnitude or more. The result also implies that in laboratory studies of ozonolysis of alkenes, the reaction of Criegee intermediate with ozone may play a role. However, this reaction would not compete with other CH$_2$OO sinks in the atmosphere.

The region 1273-1290 cm$^{-1}$ of the $\nu$4 fundamental of the simplest Criegee intermediate, CH$_2$OO, has been measured using a quantum cascade laser transient absorption spectrometer, which offers greater sensitivity and spectral resolution (< 0.004 cm$^{-1}$) than previous works based on thermal light sources. Gas phase CH$_2$OO was generated from the reaction of CH$_2$I + O2 at 298 K and 4 Torr. Analysis of the absorption spectrum has provided precise values for the vibrational frequency and the rotational constants, with fitting errors of a few MHz. The determined ratios of the rotational constants, A'/A" = 0.9986, B'/B" = 0.9974 and C'/C" = 1.0010, and the relative intensities of the a- and b-type transitions, 90:10, are in good agreement with literature values from a theoretical calculation using the MULTIMODE approach, based on a high-level ab initio potential energy surface. The low-K (= Ka) lines can be fitted extremely well, but rotational perturbations by other vibrational modes disrupt the structure for K = 4 and K $\geq$ 6. Not only the spectral resolution but also the detection sensitivity of CH$_2$OO IR transitions has been greatly improved in this work, allowing for unambiguous monitoring of CH$_2$OO in kinetic studies at low concentrations.

The understanding of molecular structure and function is at the very heart of the chemical and molecular sciences. Experiments that allow for the creation of structurally pure samples and the investigation of their molecular dynamics and chemical function have developed tremendously over the last few decades, although "there's plenty of room at the bottom" for better control as well as further applications. Here, we describe the use of inhomogeneous electric fields for the manipulation of neutral molecules in the gas-phase, \ie, for the separation of complex molecules according to size, structural isomer, and quantum state. For these complex molecules, all quantum states are strong-field seeking, requiring dynamic fields for their confinement. Current applications of these controlled samples are summarised and interesting future applications discussed., Comment: Accepted by Int. Rev. Phys. Chem

Water exists as two nuclear-spin isomers, para and ortho, determined by the overall spin of its two hydrogen nuclei. For isolated water molecules the conversion between these isomers is forbidden and they act as different molecular species. Yet, these species are not readily separable, and little is known about their specific physical and chemical properties, conversion mechanisms, or interactions. Here we demonstrate the production of isolated samples of both spin isomers in pure beams of para and ortho water, with both species in their respective absolute ground state. These single-quantum-state samples are ideal targets for unraveling spin-conversion mechanisms, for precision spectroscopy and fundamental-symmetry-breaking studies, and for spin-enhanced applications, e. g., laboratory astrophysics and -chemistry or hypersensitized NMR experiments.

Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformer-specific effects in chemical reactions [Y. P. Chang et al., Science 342, 98 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca$^+$. We observed a twofold larger rate constant for the $cis$ compared to the $trans$ conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations., Comment: 12 pages, 11 figures

We demonstrate the spatial separation of the cis- and trans-conformers of 3-fluorophenol in the gas phase based on their distinct electric dipole moments. For both conformers we create very polar samples of their lowest-energy rotational quantum states. A >95 % pure beam of trans-3-fluorophenol and a >90 % pure beam of the lowest-energy rotational states of the less polar cis-3-fluorophenol were obtained for helium and neon supersonic expansions, respectively. This is the first demonstration of the spatial separation of the lowest-energy rotational states of the least polar conformer, which is necessary for strong alignment and orientation of all individual conformers., Comment: 5 pages, 5 figures

Many molecules exhibit multiple rotational isomers (conformers) that interconvert thermally and are difficult to isolate. Consequently, a precise characterization of their role in chemical reactions has proven challenging. We have probed the reactivity of specific conformers using an experimental technique based on their spatial separation in a molecular beam by electrostatic deflection. The separated conformers react with a target of Coulomb-crystallized ions in a trap. In the reaction of Ca$^+$ with 3-aminophenol, we find a twofold larger rate constant for the \textit{cis}- compared to the \textit{trans}-conformer (differentiated by the O-H bond orientation). This result is explained by conformer-specific differences in the long-range ion-molecule interaction potentials. Our approach demonstrates the possibility of controlling reactivity through selection of conformational states., Comment: 3 figures

The Controlled Molecule Imaging group (CMI) at the Center for Free Electron Laser Science (CFEL) has developed the CMIstark software to calculate, view, and analyze the energy levels of adiabatic Stark energy curves of linear, symmetric top and asymmetric top molecules. The program exploits the symmetry of the Hamiltonian to generate fully labeled adiabatic Stark energy curves. CMIstark is written in Python and easily extendable, while the core numer- ical calculations make use of machine optimized BLAS and LAPACK routines. Calculated energies are stored in HDF5 files for convenient access and programs to extract ASCII data or to generate graphical plots are provided., Comment: 19 pages, 2 figures, a manuscript submitted to Computer Physics Communications

We demonstrate the spatial separation of the prototypical indole(H2O) clusters from the various species present in the supersonic expansion of mixtures of indole and water. The major molecular constituents of the resulting molecular beam are H2O, indole, indole(H2O), and indole(H2O)2. It is a priori not clear whether such floppy systems are amenable to strong manipulation using electric fields. Here, we have exploited the cold supersonic molecular beam and the electrostatic deflector to separate indole(H2O) from the other molecular species as well as the helium seed gas. The experimental results are quantitatively explained by trajectory simulations, which also demonstrate that the quantum-state selectivity of the process leads to samples of indole(H2O) in low-lying rotational states. The prepared clean samples of indole(H2O) are ideally suited for investigations of the stereodynamics of this complex system, including time-resolved half-collision and diffraction experiments of fixed-in-space clusters. Our findings clearly demonstrate that the hydrogen bonded indole(H2O) complex behaves as a rigid molecule under our experimental conditions and that it can be strongly deflected., Comment: 7 pages, 5 figures