Merged-Beams Study of the Reaction of Cold HD

We present a merged-beams study of reactions between HD^{+} ions, stored in the Cryogenic Storage Ring (CSR), and laser-produced ground-term C atoms. The molecular ions are stored for up to 20 s in the extreme vacuum of the CSR, where they have time to relax radiatively until they reach their vibrational ground state (within 0.5 s of storage) and rotational states with J≤3 (after 5 s). We combine our experimental studies with quasiclassical trajectory calculations based on two reactive potential energy surfaces. In contrast to previous studies with internally excited H_{2}^{+} and D_{2}^{+} ions, our results reveal a pronounced isotope effect, favoring the production of CH^{+} over CD^{+} across all collision energies, and a significant increase in the absolute rate coefficient of the reaction. Our experimental results agree well with our theoretical calculations for vibrationally relaxed HD^{+} ions in their lowest rotational states.

Assignment of the methanol OH-stretch overtone spectrum using the pattern recognition method.

We present the measurement and analysis of the 2OH stretching band of methanol between 7165 cm-1 and 7230 cm-1 cooled down to 26 ± 12 K in a buffer gas cooling experiment. Measurements were performed with a cavity ring-down spectrometer having a detection limit αmin = 2 × 10-10 cm-1. A total of 350 rovibrational transitions were assigned and 62 rovibrational transitions were tentatively assigned. This assignment was performed using the pattern recognition method developed by Rakvoský et al. [Phys. Chem. Chem. Phys., 2021, 23, 20193-20200]. In this work, we extended their method by using information on the relative intensities of the transitions to add one criterion to the validation of the assignments, allowing us to firmly assign 188 additional rovibrational transitions and to tentatively assign 14 more compared to the ir work.

Mutual neutralisation of O+ with O-: investigation of the role of metastable ions in a combined experimental and theoretical study.

The mutual neutralisation of O+ with O- has been studied in a double ion-beam storage ring with combined merged-beams, imaging and timing techniques. Branching ratios were measured at the collision energies of 55, 75 and 170 (± 15) meV, and found to be in good agreement with previous single-pass merged-beams experimental results at 7 meV collision energy. Several previously unidentified spectral features were found to correspond to mutual neutralisation channels of the first metastable state of the cation (O+(2Do), τ ≈ 3.6 hours), while no contributions from the second metastable state (O+(2Po), τ ≈ 5 seconds) were observed. Theoretical calculations were performed using the multi-channel Landau-Zener model combined with the anion centered asymptotic method, and gave good agreement with several experimentally observed channels, but could not describe well observed contributions from the O+(2Do) metastable state as well as channels involving the O(3s 5So) state.

STARGATE: A new instrument for high-resolution photodissociation spectroscopy of cold ionic species.

Spectroscopy of transient anions and radicals by gated and accelerated time-of-flight experiment is a new spectrometer developed in UCLouvain. This instrument measures high-resolution photodissociation spectra of mass-selected ions by the combination of a time-of-flight spectrometer including a specific gating, bunching, and re-referencing unit with a nanosecond pulsed dye laser, a pulsed deflection, and an energy selector. The ionic species are generated in a supersonic jet expansion by means of an electric discharge or by the impact of electrons coming from an electron gun. The versatility of the molecular systems that can be addressed by this instrument is illustrated by the presentation of mass spectra of cations, anions, and ionic clusters formed from different gas mixtures and backing pressures. The high-resolution spectrum of the A~2Σ+(002)←X~2Π3/2(000) and A~2Σ+(002)←X~2Π1/2(000) rovibronic bands of N2O+ has been measured and analyzed to provide refined molecular parameters in the A~2Σ+(002) upper state. The A~2Σ+(002)←X~2Π3/2(000) band has been used to evaluate the quality of the experimental setup in terms of rotational temperature, time of measurement for certain signal to noise ratio, and the accuracy of the determination of the wavenumber scale.

Experimental study of the proton-transfer reaction C + H2+ → CH+ + H and its isotopic variant (D2+).

We report absolute integral cross section (ICS) measurements using a dual-source merged-fast-beams apparatus to study the titular reactions over the relative translational energy range of Er ∼ 0.01-10 eV. We used photodetachment of C- to produce a pure beam of atomic C in the ground electronic 3P term, with statistically populated fine-structure levels. The H2+ and D2+ were formed in an electron impact ionization source, with well known vibrational and rotational distributions. The experimental work is complemented by a theoretical study of the CH2+ electronic system in the reactant and product channels, which helps to clarify the possible reaction mechanisms underlying the ICS measurements. Our measurements provide evidence that the reactions are barrierless and exoergic. They also indicate the apparent absence of an intermolecular isotope effect, to within the total experimental uncertainties. Capture models, taking into account either the charge-induced dipole interaction potential or the combined charge-quadrupole and charge-induced dipole interaction potentials, produce reaction cross sections that lie a factor of ∼4 above the experimental results. Based on our theoretical study, we hypothesize that the reaction is most likely to proceed adiabatically through the 14A' and 14A'' states of CH2+via the reaction C(3P) + H2+(2Σ+g) → CH+(3Π) + H(2S). We also hypothesize that at low collision energies only H2+(v ≤ 2) and D2+(v ≤ 3) contribute to the titular reactions, due to the onset of dissociative charge transfer for higher vibrational v levels. Incorporating these assumptions into the capture models brings them into better agreement with the experimental results. Still, for energies ⪅0.1 eV where capture models are most relevant, the modified charge-induced dipole model yields reaction cross sections with an incorrect energy dependence and lying ∼10% below the experimental results. The capture cross section obtained from the combined charge-quadrupole and charge-induced dipole model better matches the measured energy dependence but lies ∼30-50% above the experimental results. These findings provide important guidance for future quasiclassical trajectory and quantum mechanical treatments of this reaction.

Synchronized Fabry-Perot cavity used for enhanced sensitivity electro-optic measurements of electric fields in the microwave range.

An electro-optic (EO) sensing system for measuring free-space electric fields in the microwave range has been developed. The system is based on a phase modulation heterodyning technique using a Mach-Zehnder interferometer. In one of the arms of the interferometer, an acousto-optic frequency shifter is used to downconvert the frequency of the detected signal in order to discriminate it from parasites emitted at the external electric field frequency. The sensing part is a LiTaO3 crystal placed in a Fabry-Perot cavity. The cavity aims at enhancing the sensitivity of the measurements. Cavity-based EO setups already used in the literature propose this sensitivity enhancement at the expense of the frequency bandwidth, whereas our setup allows this without a major impact on the frequency bandwidth. Electric fields are measured at both 15 kHz and 2.4 GHz with cavities of two different finesses; the best EO phase retardation gains obtained with the cavity are 34 and 60, respectively. The minimum detectable electric field is 0.003 V⋅m-1⋅Hz-1/2.