Comb coherence-transfer and cavity ring-down saturation spectroscopy around 1.65 µm: kHz-accurate frequencies of transitions in the 2ν3 band of 12CH4.

Comb Coherence Transfer (CCT) uses a feed-forward frequency correction to transfer the optical phase of a frequency comb to the beam of a free-running diode laser. This allows the amplification of a selected comb tooth by 50 dB while adding agile and accurate frequency tuning. In the present work, SI-traceable frequency calibration and comb tooth narrowing down to 20 kHz is additionally provided by comb frequency locking to an ultrastable optical frequency reference distributed from Paris to Grenoble through the RENATER optical fiber network [Lisdat et al., Nat. Commun., 2016, 7, 12443]. We apply this CCT broadly tunable source for saturated cavity ring-down spectroscopy of ro-vibrational R0 to R10 multiplets in the 2ν3 band of 12CH4 (from 6015 to 6115 cm-1). Indeed, efficient cavity injection with large intra-cavity power build-up induces saturation of the ro-vibrational transitions at low pressure and Doppler-free Lamb dips are observed with high signal/noise. kHz-accurate transition frequencies are derived improving by three orders of magnitude previous values from spectra in the Doppler regime, which are strongly affected by line blending. While previous saturation spectroscopy investigations addressed specific 2ν3 multiplets (R6 or R9), the CCT approach allowed for a rapid coverage of the entire R0-R10 series. Measured transition frequencies are compared with experimental and theoretical line lists available in the literature.

Heterogeneous Reactions of Methane with Cl Radicals on Large ArN Clusters.

Heterogeneous chemistry on the surfaces of atmospheric particles has a wide impact on the properties and composition of the Earth's atmosphere. In laboratory studies, clusters can represent proxies to atmospheric aerosols and help to discern the individual steps in reactions on or in aerosols. We investigate the reactivity of Cl and CCl3 radicals with methane on argon clusters using the pickup method. For radical generation, we built a new pyrolysis source partially adapting the design of radical sources that utilize the supersonic expansion into a heated silicon carbide tube. Large ArN, N̅ ≈ 110, clusters were generated in a supersonic expansion, and CH4 molecules were embedded in the clusters via a pickup process followed by the uptake of the radicals produced in the pyrolysis source. The analysis of the mass spectra recorded under different experimental conditions (i.e., with the pyrolysis ON and OFF and with only one or both reactants) allowed us to identify various products of the radical reactions on ArN. We propose a sequence of reactions based on the reaction energetics. It starts with the hydrogen abstraction from CH4 by a Cl radical resulting in HCl and CH3 followed by a halogenation step where CCl4 molecules react with the available CH3 radicals, yielding CH3Cl. By analogy, the CH3Cl enters another hydrogen abstraction by Cl, producing HCl and the CH2Cl radical, which again undergoes a halogenation step with CCl4, generating CH2Cl2. Further reaction of CH2Cl2 with Cl terminates the sequence by the production of HCl and CHCl2.

Pattern recognition as a new strategy in high-resolution spectroscopy: application to methanol OH-stretch overtones.

We further develop a strategy for a line-by-line assignment of complex high-resolution overtone spectra. A search for specific line patterns in the spectrum allows to identify upper rotational states by extending the concept of ground state combination differences (GSCD). Simultaneous use of all GSCDs relating to a given upper state significantly reduces a probability of incorrect assignments. To test this approach, we have analysed a newly recorded spectrum of methanol in the first OH-stretch overtone region, 2νOH, between 7170 cm-1 and 7220 cm-1 at temperature of 19 K by combining a tunable-laser-diode absorption spectrometer with a slit-jet supersonic expansion. The spectrum consists of 1002 lines at this low temperature reflecting the fact that methanol is an asymmetric rotor with a hindered internal rotation. In total, 295 lines have been reliably assigned, representing 63% of the total intensity. Rotational energies and rotational quantum numbers for 52 upper states have been determined. Many of these states have the same quantum numbers, suggesting couplings to a manifold of 'dark' vibrational states in this overtone region.

OH-stretch overtone of methanol: empirical assignment using a two temperature technique in a supersonic jet.

This paper describes a novel approach for empirical lower state assignments in complex high resolution ro-vibrational overtone spectra of molecules with low rotational constants and complex intramolecular dynamics. Methanol, CH3OH, was chosen as a representative of such molecules - it is an asymmetric top with two non-hydrogen nuclei and hindered internal rotation leading to dense and disordered rotational structure of vibrational overtone bands. We report the first rotationally resolved methanol spectra of the OH-stretch overtone 2ν1 band using sub-Doppler diode laser spectroscopy in a supersonic jet, and describe how the combination of two temperature analysis (TTA) and analysis by ground state combination differences (GSCDs) is used to reliably identify spectral lines that originate from lowest rotational states. In the first step of the analysis, the TTA was utilized to obtain a set of possible rotational assignments for each spectral line using the line intensity variation between two different temperatures in the supersonic jet (13, and 56 K respectively). Thereafter, the GSCDs were used to confirm specific lower state assignment for those spectral lines that have been identified to have low rotational ground states by the TTA. We show that the TTA pre-selection leads to fast and reliable confirmation by GSCDs and avoids false assignments due to accidental GSCD matches. The procedure yields an important subset of reliably assigned spectral lines in the complex ro-vibrational structure that provides a convenient starting point for subsequent application of traditional spectral analysis techniques.

Microcontroller based resonance tracking unit for time resolved continuous wave cavity-ringdown spectroscopy measurements.

We present in this work a new tracking servoloop electronics for continuous wave cavity-ringdown absorption spectroscopy (cw-CRDS) and its application to time resolved cw-CRDS measurements by coupling the system with a pulsed laser photolysis set-up. The tracking unit significantly increases the repetition rate of the CRDS events and thus improves effective time resolution (and/or the signal-to-noise ratio) in kinetics studies with cw-CRDS in given data acquisition time. The tracking servoloop uses novel strategy to track the cavity resonances that result in a fast relocking (few ms) after the loss of tracking due to an external disturbance. The microcontroller based design is highly flexible and thus advanced tracking strategies are easy to implement by the firmware modification without the need to modify the hardware. We believe that the performance of many existing cw-CRDS experiments, not only time-resolved, can be improved with such tracking unit without any additional modification to the experiment.

Rotational and rovibrational spectroscopy of CH3NC of the ground and ν4 = 1 vibrational states.

The parallel vibration-rotation band ν(4) of methyl isocyanide (CH(3)NC), with a band center at 944.9 cm(-1), was studied by FTIR spectroscopy between 890 and 980 cm(-1) in order to improve the ground-state rotational constants. Such improvement is essential for the scheduled studies of excited vibrational levels and their mutual anharmonic resonances occurring at higher values of the K rotational number. Ground-state combination differences generated from this band, spanning values of J/K from 0 to 85/13, were combined with rotational data from the literature and newly measured rotational transitions, extending the J/K range from 3/0 up to 31/14, and fitted simultaneously with a fully quantitative reproduction of the data. The infrared data of the ν(4) band were analyzed together with rotational data of the ν(4) = 1 level, spanning values of J/K from 4/0 to 14/12. The fit in the approximation of an isolated vibrational state, with the transitions perturbed by weak local resonances excluded, yields reproduction of the data within experimental uncertainties.

Accurate determination of low state rotational quantum numbers (J < 4) from planar-jet and liquid nitrogen cell absorption spectra of methane near 1.4 micron.

An improved procedure for accurate determination of empirical lower state rotational quantum numbers from molecular absorption spectra is demonstrated for methane. We combine the high resolution absorption spectra in the 7070-7300 cm(-1) frequency range obtained in liquid nitrogen cooled cryogenic cell (T = 81 K) and in supersonic planar jet expansion (T(R) = 25 K). Empirical lower state energies of 59 transitions are determined from the ratio of the absolute absorption line strengths at 25 and 81 K. The procedure relies on the realistic description of rotational state populations in the supersonic jet expansion where non-equilibrium nuclear spin isomer distributions are generated due to the rapid cooling. The accuracy of the experimental determination of the lower state energies with J < or = 3 is found to considerably improve the results of the same approach applied to spectra at 296 and 81 K. The 59 transitions with determined lower J values provide a good starting point for the theoretical interpretation of the highly congested icosad region of methane. In particular, the centres of nine vibrational bands are estimated from the transitions with J = 0 lower state rotational quantum number.

Solvent-induced photostability of acetylene molecules in clusters probed by multiphoton dissociation.

We have studied the multiphoton photodissociation of (C(2)H(2))(n) and (C(2)H(2))(n) x Ar(m) clusters in molecular beams. The clusters were prepared in supersonic expansions under various conditions, and the corresponding mean cluster sizes were determined, for which the photodissociation at 193 nm was studied. The measured kinetic energy distributions (KEDs) of the H fragment from acetylene in clusters peak around 0.2 eV, in agreement with the KED from an isolated C(2)H(2) molecule. However, the KEDs from the clusters extend to kinetic energies of over 2 eV, significantly higher than the maximum fragment energies from an isolated molecule of about 1 eV. The photofragment acceleration upon solvation is a rather unusual phenomenon. The analysis based on ab initio calculations suggests the following scenario: (i) At 193 nm, photodissociation of acetylene occurs mostly in the singlet manifold. (ii) The solvent stabilizes the acetylene molecule, preventing it from undergoing hydrogen dissociation and funneling the population into a vibrationally hot ground state. (iii) The excited C(2)H(2) absorbs the next photon and eventually dissociates, yielding the H fragment with a higher kinetic energy corresponding to the first C(2)H(2) excitation. Thus, the H-fragment KED extending to higher energies is a fingerprint of the cage effect and the multiphoton nature of the observed processes. The photon-flux dependence of the KEDs reflects the rate of the vibrational energy flow from the hot ground state of acetylene to the neighboring solvent molecules.

Generation and orientation of organoxenon molecule H-Xe-CCH in the gas phase.

We report on the first observation of the organoxenon HXeCCH molecule in the gas phase. This molecule has been prepared in a molecular beam experiment by 193 nm photolysis of an acetylene molecule on Xe(n) clusters (n approximately 390). Subsequently the molecule has been oriented via the pseudo-first-order Stark effect in a strong electric field of the polarized laser light combined with the weak electrostatic field in the extraction region of a time-of-flight spectrometer. The experimental evidence for the oriented molecule has been provided by measurements of its photodissociation. For comparison, photolysis of C(2)H(2) on Ar(n) clusters (n approximately 280) has been measured. Here the analogous rare gas molecule HArCCH could not be generated. The interpretation of our experimental findings has been supported by ab initio calculations. In addition, the experiment together with the calculations reveals information on the photochemistry of the HXeCCH molecule. The 193 nm radiation excites the molecule predominantly into the 2 (1)Sigma(+) state, which cannot dissociate the Xe-H bond directly, but the system evolves along the Xe-C coordinate to a conical intersection of a slightly nonlinear configuration with the dissociative 1 (1)Pi state, which then dissociates the Xe-H bond.

Pulsed oscillating mass spectrometer: a miniaturized type of time-of-flight mass spectrometer.

We report the development, characterization, and performance of a new type of time-of-flight mass analyzer that employs an oscillatory ion flight path and uses secondary electrons to record the mass spectrum. The analyzer is simple in concept and design and inexpensive to build and has been made as small as 6-cm total length. The oscillating ions produce a periodic secondary electron signal whose frequency is mass dependent in mathematically the same way as a conventional time-of-flight analyzer. Because of the oscillating nature of the ions, we have called the analyzer the pulsed oscillating mass spectrometer.

Intracluster stereochemistry in van der Waals complexes: steric effects in ultraviolet photodissociation of state-selected Ar-HOD/H2O.

High-resolution IR-UV multiple resonance methods are employed to elucidate the photodissociation dynamics of quantum state-selected Ar-HOD and Ar-H(2)O van der Waals clusters. A single mode pulsed OPO operating in the region of the OH second overtone is used to prepare individual rovibrational states that are selectively photodissociated at specific excimer wavelengths. Subsequent fluorescence excitation of the resulting OH (OD) fragments yields dynamical information on the photofragmentation event and any resulting intracluster collisions. This technique is used to characterize spectroscopically the Pi(1(01)), nu(OH)=3<--Sigma(0(00)), v(OH)=0 overtone band of the Ar-HOD complex with an origin at 10648.27 cm(-1). The effects of Ar complexation on the dissociation dynamics are inferred by comparison of the OD photofragment quantum state distributions resulting from dissociation of single rovibrational states of the complex with those from isolated HOD photodissociation. The important role played by the initial internal state of the complex is demonstrated by comparison of the current Ar-HOD data with previously published results for the Ar-H(2)O Sigma(0(00))[03(-)> state. We interpret the dramatic differences in the dynamics of the two systems as manifestations of the nodal structure of the vibrational state in the parent complex and the way in which it governs the collision probability between the Ar atom and the escaping photofragments.