| 1. |
- Anderson, Emma K., 1986-, et al.
(författare)
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Fragmentation of and electron detachment from hot copper and silver dimer anions : A comparison
- 2023
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Ingår i: Physical Review A: covering atomic, molecular, and optical physics and quantum information. - 2469-9926 .- 2469-9934. ; 107:6
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Tidskriftsartikel (refereegranskat)abstract
- We measured the spontaneous decays of internally hot copper and silver dimer anions, and , stored in one of the two ion-beam storage rings of the Double Electrostatic Ion Ring Experiment (DESIREE) at Stockholm University. A coincidence detection technique was utilized enabling essentially background-free measurements of -> Cu + Cu- and -> Ag + Ag- fragmentation rates. Furthermore, the total rates of neutral decay products (monomers and dimers) were measured and the relative contributions of fragmentation and electron emission ( -> Cu2 + e- and -> Ag2 + e-) were deduced as functions of storage time. Fragmentation is completely dominant at early times. However, after about 20 ms of storage, electron emission is observed and becomes the leading decay path after 100 ms for both dimer anions. The branching ratios between fragmentation and electron emission (vibrationally assisted autodetachment processes) are very nearly the same for and Ag-2 throughout the present storage cycle of 10 seconds. This is surprising considering the difference between the electron affinities of the neutral dimers, Cu2 and Ag2, and the difference between the and the dissociation energies.
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| 2. |
- Bernard, Jérôme, et al.
(författare)
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Efficient radiative cooling of tetracene cations C18H12+ : absolute recurrent fluorescence rates as a function of internal energy
- 2023
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 25:15, s. 10726-10740
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Tidskriftsartikel (refereegranskat)abstract
- We have measured recurrent fluorescence (RF) cooling rates of internally hot tetracene cations, C18H12+, as functions of their storage times and internal energies in two different electrostatic ion-beam storage rings – the cryogenic ring DESIREE with a circumference of 8.6 meters in Stockholm and the much smaller room temperature ring Mini-Ring in Lyon, which has a circumference of 0.71 meters. The RF rates were measured to be as high as 150 to 1000 s−1 for internal energies in the 7 to 9.4 eV energy range, where we have probed the time evolution of the internal energy distribution with nanosecond laser pulses with a 1 kHz repetition rate. These RF rates are found to be significantly higher than those of previously investigated smaller PAHs such as e.g. anthracene and naphthalene, for which the lowest non-forbidden electronic excited state, the D2 state, is populated with a smaller probability by inverse internal conversion. Furthermore, the D2–D0 transition rate is smaller for these smaller molecules than for tetracene. The complementary features of the two storage rings allow for RF rate measurements in a broader internal energy range than has been possible before. The smaller sampling period of about 6 μs in Mini-Ring is ideal to study the cooling dynamics of the hotter ions that decay fast, whereas DESIREE with a sampling period of about 60 μs is better suited to study the colder ions that decay on longer timescales ranging up to hundreds of milliseconds. The excellent agreement between the two series of measurements in the region where they overlap demonstrates the complementarity of the two electrostatic ion-beam storage rings.
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| 3. |
- Bogot, Alon, et al.
(författare)
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The mutual neutralization of hydronium and hydroxide
- 2024
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Ingår i: Science. - 0036-8075 .- 1095-9203. ; 383:6680, s. 285-289
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Tidskriftsartikel (refereegranskat)abstract
- Mutual neutralization of hydronium (H3O+) and hydroxide (OH−) ions is a very fundamental chemical reaction. Yet, there is only limited experimental evidence about the underlying reaction mechanisms. Here, we report three-dimensional imaging of coincident neutral products of mutual-neutralization reactions at low collision energies of cold and isolated ions in the cryogenic double electrostatic ion-beam storage ring (DESIREE). We identified predominant H2O + OH + H and 2OH + H2 product channels and attributed them to an electron-transfer mechanism, whereas a minor contribution of H2O + H2O with high internal excitation was attributed to proton transfer. The reported mechanism-resolved internal product excitation, as well as collision-energy and initial ion-temperature dependence, provide a benchmark for modeling charge-transfer mechanisms.
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| 4. |
- Gatchell, Michael, 1988-, et al.
(författare)
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Stability of C59 Knockout Fragments from Femtoseconds to Infinity
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- We have studied the stability of C59 anions as a function of time, from their formation on femtosecond timescales to their stabilization on second timescales and beyond, using a combination of theory and experiments. The C59 fragments were produced in collisions between C60 fullerene anions and neutral helium gas at a velocity of 90 km/s (corresponding to a collision energy of 166 eV in the center-of-mass frame). The fragments were then stored in a cryogenic ion-beam storage ring at the DESIREE facility where they were followed for up to one minute. Classical molecular dynamics simulations were used to determine the reaction cross section and the excitation energy distributions of the products formed in these collisions. We found that about 15 percent of the C59 ions initially stored in the ring are intact after about 100 ms, and that this population then remains intact indefinitely. This means that C60 fullerenes exposed to energetic atoms and ions, such as stellar winds and shock waves, will produce stable, highly reactive products, like C59, that are fed into interstellar chemical reaction networks.
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| 5. |
- Gatchell, Michael, 1988-, et al.
(författare)
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Stability of C59 Knockout Fragments from Femtoseconds to Infinity
- 2024
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Ingår i: Astrophysical Journal. - 0004-637X .- 1538-4357. ; 966:2
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the stability of C59 anions as a function of time, from their formation on femtosecond timescales to their stabilization on second timescales and beyond, using a combination of theory and experiments. The C-59 fragments were produced in collisions between C60 fullerene anions and neutral helium gas at a velocity of 90 km s−1 (corresponding to a collision energy of 166 eV in the center-of-mass frame). The fragments were then stored in a cryogenic ion beam storage ring at the DESIREE facility, where they were followed for up to 1 minute. Classical molecular dynamics simulations were used to determine the reaction cross section and the excitation energy distributions of the products formed in these collisions. We find that about 15% of the C-59 ions initially stored in the ring are intact after about 100 ms and that this population then remains intact indefinitely. This means that C60 fullerenes exposed to energetic atoms and ions, such as stellar winds and shock waves, will produce stable, highly reactive products, like C59, that are fed into interstellar chemical reaction networks.
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| 6. |
- Lee, Jason W. L., et al.
(författare)
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Cooling dynamics of energized naphthalene and azulene radical cations
- 2023
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Ingår i: Journal of Chemical Physics. - 0021-9606 .- 1089-7690. ; 158:17
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Tidskriftsartikel (refereegranskat)abstract
- Naphthalene and azulene are isomeric polycyclic aromatic hydrocarbons (PAHs) and are topical in the context of astrochemistry due to the recent discovery of substituted naphthalenes in the Taurus Molecular Cloud-1 (TMC-1). Here, the thermal- and photo-induced isomerization, dissociation, and radiative cooling dynamics of energized (vibrationally hot) naphthalene (Np+) and azulene (Az(+)) radical cations, occurring over the microsecond to seconds timescale, are investigated using a cryogenic electrostatic ion storage ring, affording molecular cloud in a box conditions. Measurement of the cooling dynamics and kinetic energy release distributions for neutrals formed through dissociation, until several seconds after hot ion formation, are consistent with the establishment of a rapid (sub-microsecond) Np+ reversible arrow Az(+) quasi-equilibrium. Consequently, dissociation by C2H2-elimination proceeds predominantly through common Az(+) decomposition pathways. Simulation of the isomerization, dissociation, recurrent fluorescence, and infrared cooling dynamics using a coupled master equation combined with high-level potential energy surface calculations [CCSD(T)/cc-pVTZ], reproduce the trends in the measurements. The data show that radiative cooling via recurrent fluorescence, predominately through the Np+ D-0 <- D-2 transition, efficiently quenches dissociation for vibrational energies up to approximate to 1 eV above dissociation thresholds. Our measurements support the suggestion that small cations, such as naphthalene, may be more abundant in space than previously thought. The strategy presented in this work could be extended to fingerprint the cooling dynamics of other PAH ions for which isomerization is predicted to precede dissociation.
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| 7. |
- Najeeb, P. K., 1986-, et al.
(författare)
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Stability and Cooling of the C72- Dianion
- 2023
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 131:11
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the stability of the smallest long-lived all carbon molecular dianion (C72-) in new time domains and with a single ion at a time using a cryogenic electrostatic ion-beam storage ring. We observe spontaneous electron emission from internally excited dianions on millisecond timescales and monitor the survival of single colder C72- molecules on much longer timescales. We find that their intrinsic lifetime exceeds several minutes - 6 orders of magnitude longer than established from earlier experiments on C72-. This is consistent with our calculations of vertical electron detachment energies predicting one inherently stable isomer and one isomer which is stable or effectively stable behind a large Coulomb barrier for C72-→C7-+e- separation.
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| 8. |
- Najeeb, P. K., 1986-, et al.
(författare)
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Stability and Cooling of the C2−7 Dianion
- 2023
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 131:11
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Tidskriftsartikel (refereegranskat)abstract
- We have studied the stability of the smallest long-lived all carbon molecular dianion () in new time domains and with a single ion at a time using a cryogenic electrostatic ion-beam storage ring. We observe spontaneous electron emission from internally excited dianions on millisecond timescales and monitor the survival of single colder molecules on much longer timescales. We find that their intrinsic lifetime exceeds several minutes—6 orders of magnitude longer than established from earlier experiments on . This is consistent with our calculations of vertical electron detachment energies predicting one inherently stable isomer and one isomer which is stable or effectively stable behind a large Coulomb barrier for →+e− separation.
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| 9. |
- Navarro Navarrete, José E., 1988-, et al.
(författare)
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Experimental radiative cooling rates of a polycyclic aromatic hydrocarbon cation
- 2023
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Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 245, s. 352-367
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Tidskriftsartikel (refereegranskat)abstract
- Several small Polycyclic Aromatic Hydrocarbons (PAHs) have been identified recently in the Taurus Molecular Cloud (TMC-1) using radio telescope observations. Reproducing the observed abundances of these molecules has been a challenge for astrochemical models. Rapid radiative cooling of PAHs by Recurrent Fluorescence (RF), the emission of optical photons from thermally populated electronically excited states, has been shown to efficiently stabilize small PAHs following ionization, augmenting their resilience in astronomical environments and helping to rationalize their observed high abundances. Here, we use a novel method to experimentally determine the radiative cooling rate of the cation of 1-cyanonaphthalene (C10H7CN, 1-CNN), the neutral species of which has been identified in TMC-1. Laser-induced dissociation rates and kinetic energy release distributions of 1-CNN cations isolated in a cryogenic electrostatic ion-beam storage ring are analysed to track the time evolution of the vibrational energy distribution of the initially hot ion ensemble as it cools. The measured cooling rate is in good agreement with the previously calculated RF rate coefficient. Improved measurements and models of the RF mechanism are needed to interpret astronomical observations and refine predictions of the stabilities of interstellar PAHs.
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| 10. |
- Poline, Mathias, et al.
(författare)
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Mutual neutralisation of O+ with O− : investigation of the role of metastable ions in a combined experimental and theoretical study
- 2021
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 23:43, s. 24607-24616
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Tidskriftsartikel (refereegranskat)abstract
- 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.
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