More Like this

1. Radiative double-electron capture by fully stripped and one-electron ions in gas and thin-foil targets

   Tanis, John A ( September 2021 , Physical review)

   null (Ed.)

   Radiative double-electron capture (RDEC), in which two-electron capture is accompanied by simultaneousemission of a single photon, was investigated for fully stripped and one-electron projectiles colliding withgaseous and thin-foil targets. RDEC can be considered the inverse of double photoionization by a single photon.For the gaseous targets, measurements were done for 2.11 MeV/uF9+and F8+ions interacting with N2and Ne,while for the thin-foil target the measurements were done for 2.11 MeV/uF9+and F8+and 2.19 MeV/uO8+andO7+ions striking thin C targets. Reports on this work were already published separately in shorter accounts by LaMantiaet al.[Phys. Rev. Lett.124, 133401 (2020)for the gas targets andPhys.Rev.A102, 060801(R) (2020)forthe thin-foil targets]. The gas targets were studied under single-collision conditions, while the foil targets sufferedunavoidable multiple collisions. The measurements were carried out by detecting x-ray emission from the targetat 90◦to the beam direction in coincidence with outgoing ions undergoing double, single, and, in the caseof the foil targets, no charge change inside the target. Striking differences between the gaseous and foil targetswere found from these measurements, with RDEC for the gaseous targets occurring only in coincidence with q-2outgoing projectiles as expected, while RDEC for the foil targets was seen in each of the outgoing q-2, q-1, and nocharge-change states. The no charge-change result was totally unexpected. The cross sections for RDEC for thefully stripped ions on gas targets were found to be about six times larger than those for the one-electron projec-tiles. For the foil targets, the RDEC cross sections for the fully stripped and one-electron projectiles differ some-what from one another but not to the the extent they did for the gas targets. In this work the cross sections for allof the projectiles for the foil targets were adjusted due to the target contaminant background from potassium andcalcium atoms that existed in the spectra. Also, the cross sections for the incident one-electron projectiles weremodified due to a correction for the fraction of these ions that becomes fully stripped in passage through the foil.These differences are attributed to the effects of the multiple collisions that occur for the foil targets. The differ-ential cross sections at 90◦determined for each of the projectiles interacting with each of the targets are comparedwith each other and with the previous measurements. To the extent that the cross sections follow a sin2θdepen-dence, the total cross sections are compared with theoretical calculations [E. A. Mistonova and O. Yu. Andreev,Phys. Rev. A87, 034702 (2013)], for which the agreement is poor, with the measured cross section exceedingthe predicted ones by about an order of magnitude. Possible reasons for this discrepancy will be discussed. 

   more » « less
2. Single and double electron capture associated with target K‐shell ionization for F 7 + ,8 + ,9+ +Ar

   https://doi.org/10.1002/xrs.3053  

   La Mantia, David ; Kumara, P. N. S. ; Kayani, Asghar ; Tanis, John ( May 2019 , X-Ray Spectrometry)

   Ratios for target Ar K‐shell ionization associated with single and double electron capture, as well as the ratios corresponding to total capture and the projectile K x rays, were determined for 1.8‐ to 2.2‐MeV/u F^{7 + ,8 + ,9+}projectiles. This work was performed at Western Michigan University with the tandem Van de Graaff accelerator. Coincidences between emitted K‐shell X‐rays (both target and projectile) and the corresponding charge‐changed particles were observed. The F⁹⁺Ar K X‐ray coincidence ratios for double to single capture are found to well exceed unity over the limited energy range of the measurements. Possible explanations for this anomalous behavior are discussed.

    

   more » « less
3. An ion mobility mass spectrometer coupled with a cryogenic ion trap for recording electronic spectra of charged, isomer-selected clusters

   https://doi.org/10.1063/5.0085680  

   Buntine, Jack T. ; Carrascosa, Eduardo ; Bull, James N. ; Jacovella, Ugo ; Cotter, Mariah I. ; Watkins, Patrick ; Liu, Chang ; Scholz, Michael S. ; Adamson, Brian D. ; Marlton, Samuel J. P. ; et al ( April 2022 , Review of Scientific Instruments)

   Infrared and electronic spectra are indispensable for understanding the structural and energetic properties of charged molecules and clusters in the gas phase. However, the presence of isomers can potentially complicate the interpretation of spectra, even if the target molecules or clusters are mass-selected beforehand. Here, we describe an instrument for spectroscopically characterizing charged molecular clusters that have been selected according to both their isomeric form and their mass-to-charge ratio. Cluster ions generated by laser ablation of a solid sample are selected according to their collision cross sections with helium buffer gas using a drift tube ion mobility spectrometer and their mass-to-charge ratio using a quadrupole mass filter. The mobility- and mass-selected target ions are introduced into a cryogenically cooled, three-dimensional quadrupole ion trap where they are thermalized through inelastic collisions with an inert buffer gas (He or He/N₂mixture). Spectra of the molecular ions are obtained by tagging them with inert atoms or molecules (Ne and N₂), which are dislodged following resonant excitation of an electronic transition, or by photodissociating the cluster itself following absorption of one or more photons. An electronic spectrum is generated by monitoring the charged photofragment yield as a function of wavelength. The capacity of the instrument is illustrated with the resonance-enhanced photodissociation action spectra of carbon clusters ([Formula: see text]) and polyacetylene cations (HC_{2 n}H⁺) that have been selected according to the mass-to-charge ratio and collision cross section with He buffer gas and of mass-selected [Formula: see text] and Au₂Ag⁺clusters.

    

   more » « less
4. Quantum electronic control on chemical activation of methane by collision with spin–orbit state selected vanadium cation

   https://doi.org/10.1039/D0CP04333H  

   Ng, Cheuk-Yiu ; Xu, Yuntao ; Chang, Yih-Chung ; Wannenmacher, Anna ; Parziale, Matthew ; Armentrout, P. B. ( January 2021 , Physical Chemistry Chemical Physics)

   null (Ed.)

   By coupling a newly developed quantum-electronic-state-selected supersonically cooled vanadium cation (V + ) beam source with a double quadrupole-double octopole (DQDO) ion–molecule reaction apparatus, we have investigated detailed absolute integral cross sections ( σ 's) for the reactions, V + [a 5 D J ( J = 0, 2), a 5 F J ( J = 1, 2), and a 3 F J ( J = 2, 3)] + CH 4 , covering the center-of-mass collision energy range of E cm = 0.1–10.0 eV. Three product channels, VH + + CH 3 , VCH 2 + + H 2 , and VCH 3 + + H, are unambiguously identified based on E cm -threshold measurements. No J -dependences for the σ curves ( σ versus E cm plots) of individual electronic states are discernible, which may indicate that the spin–orbit coupling is weak and has little effect on chemical reactivity. For all three product channels, the maximum σ values for the triplet a 3 F J state [ σ (a 3 F J )] are found to be more than ten times larger than those for the quintet σ (a 5 D J ) and σ (a 5 F J ) states, showing that a reaction mechanism favoring the conservation of total electron spin. Without performing a detailed theoretical study, we have tentatively interpreted that a weak quintet-to-triplet spin crossing is operative for the activation reaction. The σ (a 5 D 0 , a 5 F 1 , and a 3 F 2) measurements for the VH + , VCH 2 + , and VCH 3 + product ion channels along with accounting of the kinetic energy distribution due to the thermal broadening effect for CH 4 have allowed the determination of the 0 K bond dissociation energies: D 0 (V + –H) = 2.02 (0.05) eV, D 0 (V + –CH 2 ) = 3.40 (0.07) eV, and D 0 (V + –CH 3 ) = 2.07 (0.09) eV. Detailed branching ratios of product ion channels for the titled reaction have also been reported. Excellent simulations of the σ curves obtained previously for V + generated by surface ionization at 1800–2200 K can be achieved by the linear combination of the σ (a 5 D J , a 5 F J , and a 3 F J ) curves weighted by the corresponding Boltzmann populations of the electronic states. In addition to serving as a strong validation of the thermal equilibrium assumption for the populations of the V + electronic states in the hot filament ionization source, the agreement between these results also confirmed that the V + (a 5 D J , a 5 F J , and a 3 F J ) states prepared in this experiment are in single spin–orbit states with 100% purity. 

   more » « less
5. Solar‐induced chlorophyll fluorescence and short‐term photosynthetic response to drought

   https://doi.org/10.1002/eap.2101  

   Helm, Levi T. ; Shi, Hanyu ; Lerdau, Manuel T. ; Yang, Xi ( March 2020 , Ecological Applications)

   Drought is among the most damaging climate extremes, potentially causing significant decline in ecosystem functioning and services at the regional to global scale, thus monitoring of drought events is critically important. Solar‐induced chlorophyll fluorescence (SIF) has been found to strongly correlate with gross primary production on the global scale. Recent advances in the remote sensing of SIF allow for large‐scale, real‐time estimation of photosynthesis using this relationship. However, several studies have used SIF to quantify the impact of drought with mixed results, and the leaf‐level mechanisms linking SIF and photosynthesis are unclear, particularly how the relationship may change under drought. We conducted a drought experiment with 2‐yr oldPopulus deltoides. We measured leaf‐level gas exchange, SIF, and pulse amplitude modulated (PAM) fluorescence before and during the 1‐month drought. We found clear responses of net photosynthesis and stomatal conductance to water stress, however, SIF showed a smaller response to drought. Net photosynthesis (A_net) and conductance dropped 94% and 95% on average over the drought, while SIF values only decreased slightly (21%). Electron transport rate dropped 64% when compared to the control over the last week of drought, but the electron transport chain did not completely shut down asA_netapproached zero. Additionally, SIF yield (SIF_y) was positively correlated with steady‐state fluorescence (F_s) and negatively correlated with non‐photochemical quenching (NPQ;R² = 0.77). BothF_sand SIF_y, after normalization by the minimum fluorescence from a dark‐adapted sample (F_o), showed a more pronounced drought response, although the results suggest the response is complicated by several factors. Leaf‐level experiments can elucidate mechanisms behind large‐scale remote sensing observations of ecosystem functioning. The value of SIF as an accurate estimator of photosynthesis may decrease during mild stress events of short duration, especially when the response is primarily stomatal and not fully coupled with the light reactions of photosynthesis. We discuss potential factors affecting the weak SIF response to drought, including upregulation of NPQ, change in internal leaf structure and chlorophyll concentration, and photorespiration. The results suggest that SIF is mainly controlled by the light reactions of photosynthesis, which operate on different timescales than the stomatal response.

    

   more » « less