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We have measured the kinetic energy distributions for the mutual neutralization of a large ensemble of atomic anions and cations. Ions are accelerated to equal velocities in a merged beam setup, enabling measurements at collision energies as low as 5 meV. Three-dimensional momentum imaging is performed with two position sensitive detectors located several meters downstream from the few centimeter long region where the beams overlap. An unprecedented resolution in the kinetic energy release (KER) spectra allows us to identify the states of both reactants and products down to their fine structure. Knowing the angular distribution of the products in the laboratory and center-of-mass frame, allows for total, partial, and differential cross sections to be retrieved., SCOPUS: cp.p, info:eu-repo/semantics/published

A sputter ion source with a solid graphite target has been used to produce dianions with a focus on carbon cluster dianions, $\text{C}_{n}^{2-}$, with $n=7-24$. Singly and doubly charged anions from the source were accelerated together to kinetic energies of 10 keV per atomic unit of charge and injected into one of the cryogenic (13 K) ion-beam storage rings of the Double ElectroStatic Ion Ring Experiment facility at Stockholm University. Spontaneous decay of internally hot $\text{C}_{n}^{2-}$ dianions injected into the ring yielded $\text{C}^{-}$ anions with kinetic energies of 20 keV, which were counted with a microchannel plate detector. Mass spectra produced by scanning the magnetic field of a $90^{\circ}$ analyzing magnet on the ion injection line reflect the production of internally hot $\text{C}_{7}^{2-}-\text{C}_{24}^{2-}$ dianions with lifetimes in the range of tens of microseconds to milliseconds. In spite of the high sensitivity of this method, no conclusive evidence of $\text{C}_{6}^{2-}$ was found while there was a clear $\text{C}_{7}^{2-}$ signal with the expect isotopic distribution. An upper limit is deduced for a $\text{C}_{6}^{2-}$ signal that is two orders-of-magnitue smaller than that for $\text{C}_{7}^{2-}$. In addition, $\text{C}_{n}\text{O}^{2-}$ and $\text{CsCu}^{2-}$ dianions were detected., Comment: 6 pages, 6 figures

We apply near-threshold laser photodetachment to characterize the rotational quantum level distribution of OH- ions stored in the cryogenic ion-beam storage ring DESIREE at Stockholm University. We ...

Synopsis The decay of hot copper dimer anions is studied in a cryogenic storage ring. We detect atomic anion and neutral products and determine the fragmentation and vibrational autodetachment (VAD) rates separately. For short storage times the dimer anions predominantly decay by fragmentation of highly rotationally excited ions by tunneling through the rotational barrier. For storage times exceeding 100 ms, however, VAD is dominating. This process is driven by the very weak direct coupling between nuclear and electronic degrees of freedom.

We have measured the spontaneous neutral particle emission from copper-cluster anions (${\mathrm{Cu}}_{n}{}^{\ensuremath{-}}, n=3--6$) stored at cryogenic temperatures in one of the electrostatic ion storage rings of the Double ElectroStatic Ion Ring ExpEriment facility at Stockholm University. The measured rate of emission from the stored ${\mathrm{Cu}}_{3}{}^{\ensuremath{-}}$ ions follows a single power-law decay for about 1 ms but then decreases much more rapidly with time. The latter behavior may be due to a decrease in the density of available final states in ${\mathrm{Cu}}_{3}$ as the excitation energies of the decaying ions approach the electron detachment threshold. The emissions from ${\mathrm{Cu}}_{4}{}^{\ensuremath{-}}, {\mathrm{Cu}}_{5}{}^{\ensuremath{-}}$, and ${\mathrm{Cu}}_{6}{}^{\ensuremath{-}}$ are well described by sums of two power laws that are quenched by radiative cooling of the stored ions with characteristic times between a few and hundreds of milliseconds. We relate these two-component behaviors to populations of stored ions with higher and lower angular momenta. In a separate experiment, we studied the laser-induced decay of ${\mathrm{Cu}}_{6}{}^{\ensuremath{-}}$ ions that were excited by 1.13- or 1.45-eV photons after 46 ms of storage.

The intrinsic radiative lifetimes of the $5{d}^{10}6{s}^{}^{2}S_{1/2}$ and $5{d}^{9}6{s}^{2} ^{2}D_{3/2}$ bound excited states in the platinum anion ${\text{Pt}}^{\ensuremath{-}}$ have been studied at cryogenic temperatures at the Double ElectroStatic Ion Ring Experiment (DESIREE) facility at Stockholm University. The intrinsic lifetime of the higher-lying $5{d}^{10}6{s}^{} ^{2}S_{1/2}$ state was measured to be $2.54\ifmmode\pm\else\textpm\fi{}0.10\phantom{\rule{0.16em}{0ex}}\mathrm{s}$, while only a lifetime in the range of 50\char21{}200 ms could be estimated for the $5{d}^{9}6{s}^{2} ^{2}D_{3/2}$ fine-structure level. The storage lifetime of the ${\text{Pt}}^{\ensuremath{-}}$ ion beam was measured to be a little over 15 min at a ring temperature of $13\phantom{\rule{0.16em}{0ex}}\mathrm{K}$. The present study reports the lifetime of an atomic negative ion in an excited bound state with an electron configuration different from that of the ground state.

Nitrile ions are abundant in Titan's upper atmosphere and are expected to be lost mainly via dissociative recombination with free electrons. We review in this paper a series of experimental results ...

We have investigated the dissociative recombination (DR) of the C 6 D 6 + and C 6 D 7 + ions using the CRYRING heavy-ion storage ring at Stockholm University, Sweden. The dissociative recombination branching ratios were determined at minimal collision energy, showing that the DR of both ions was dominated by pathways keeping the carbon atoms together in one product. The absolute reaction cross sections for the titular ions are best fitted by σ (E cm [eV]) = 1.3 ± 0.4 × 10 -15 (E cm [eV]) −1.19 ± 0.02 cm 2 (C 6 D 6 + ) and σ (E cm [eV]) = 1.1 ± 0.3 × 10 -15 (E cm [eV]) −1.33 ± 0.02 cm 2 (C 6 D 7 + ) in the intervals 3-300 meV and 3-200 meV respectively. The thermal rate constants of the titular reactions are best described by: k(T) = 1.3 ± 0.4 × 10 -6 (T/300) −0.69 ± 0.02 cm 3 s -1 for C 6 D 6 + and k(T) = 2.0 ± 0.6 × 10 -6 (T/300) −0.83 ± 0.02 cm 3 s -1 for C 6 D 7 + . These expressions correlates well with earlier flowing afterglow studies on the same process.

The dissociative recombination of protonated propionitrile, CH3CH2CNH+, has been investigated at the heavy ion storage ring, CRYRING, at the Manne Siegbahn Laboratory, Stockholm University, Sweden. ...

Measurements on the dissociative recombination (DR) of protonated acrylonitrile, CH2CHCNH+, have been performed at the heavy ion storage ring CRYRING located in the Manne Siegbahn Laboratory in Stockholm, Sweden. It has been found that at~2meV relative kinetic energy about 50% of the DR events involve only ruptures of X–H bonds (where X=C or N)while the rest leads to the production of a pair of fragments each containing two heavy atoms (alongside H and/or H2). The absolute DR cross section has been investigated for relative kinetic energies ranging from ~1 meV to 1 eV. The thermal rate coefficient has been determined to follow the expression k(T) = 1.78 × 10-6 (T/300)-0.80 cm3 s-1 for electron temperatures ranging from ~10 to 1000 K. Gas-phase models of the nitrile chemistry in the dark molecular cloud TMC-1 have been run and results are compared with observations. Also, implications of the present results for the nitrile chemistry of Titan’s upper atmosphere are discussed.

The intrinsic lifetime of the upper level in the bound-bound $3{d}^{9}\phantom{\rule{0.16em}{0ex}}4{s}^{2}$ ${}^{2}{D}_{3/2} \ensuremath{\rightarrow} 3{d}^{9}\phantom{\rule{0.16em}{0ex}}4{s}^{2}$ ${}^{2}{D}_{5/2}$ radiative transition in ${\text{Ni}}^{\ensuremath{-}}$ was measured to be $15.1\ifmmode\pm\else\textpm\fi{}0.4\phantom{\rule{0.16em}{0ex}}\mathrm{s}$. The experiment was performed at cryogenic temperatures in one of the ion-beam storage rings of the Double ElectroStatic Ion Ring ExpEriment facility at Stockholm University. The storage lifetime of the ${\text{Ni}}^{\ensuremath{-}}$ ion beam was measured to be close to 5 min at a ring temperature of 13 K.

(2007). Experimental determination of dissociative recombination reaction pathways and absolute reaction cross-sections of CH2OH + , CD2OD + and CD2. Molecular Physics: Vol. 105, A Special Issue In Honour of John M. Brown, pp. 899-906.

We use a novel electrostatic ion storage ring to measure the radiative lifetime of the upper level in the 3p 5 P 2 o 1/2 →3p 5 P 2 o 3/2 spontaneous radiative decay in S − 32 to be 503±54 ...

Branching ratios and absolute cross sections have been measured for the dissociative recombination of HCS+ and OCS+ at the CRYRING ion storage ring. In the case of OCS+, the channel leading to CO + S (83%) dominates, whereas the other exoergic pathways leading to CS + O (14%) and C + SO (3%) are of lesser importance. In the case of HCS+, fracture of the C–S bond is predominant (81%), with the production of H + CS accounting for the remainder (19%). The cross section of the reaction could be fitted by the expressions σ = 1.41 × 10-15E(eV)-1.11 and 4.47 × 10-16E(eV)-1.14 cm2 for HCS+ and OCS+, respectively. The derived energy dependences of the thermal reaction rate coefficients can be fitted by k(T) = 9.7 × 10-7(T/300)-0.57 and 3.5 × 10-7(T/300)-0.62 cm3 s-1 for HCS+ and OCS+, respectively. We use these data to perform model calculations on the HCS+/CS abundance ratio in dark clouds and find that the models using the UMIST and Ohio State University databases have even more difficulty in accounting for the large observed ratio.

The dissociative recombination and excitation of CF+ have been measured at the ASTRID and CRYRING storage rings. Though examination of the available potential energy curves would suggest that the recombination rate would be large for this ion, in fact a rate constant of 5.2 ± 1.0 × 10−8 (Te/300)−0.8 cm3 s−1 was found. The recombination cross section at low energies falls off to a minimum at 0.5 eV centre-of-mass collision energy but exhibits resonances at energies above this. The dissociative excitation cross section leading to C+ + F was also measured and this displays an onset beginning at about 7 eV.

Cross sections and branching ratios for the dissociative recombination (DR) reactions of the astrophysically important ions HN2+, HCO+, DOCO+, and SO2+ at reactant kinetic energies from 1 to 1000 meV have been measured using the CRYRING ion storage ring facility at the Manne Siegbahn Laboratory, Stockholm University. Whereas the break-up of the N-N bond leading to NH + N is the major pathway in the DR of HN2+, the analogous reaction in HCO+ almost exclusively leads to H and CO. In the DR of both DOCO+ and SO2+ three-body break-up was observed. Inclusion of the newly measured branching ratios into a standard model on dark interstellar clouds leads to an improvement of the predictions of such models, especially concerning the abundances of nitrogen compounds. The impact of these newly found branching ratios and reaction rates on the chemistry of different astronomical environments like dark clouds, circumstellar envelopes and planetary ionospheres, is discussed.

Branching ratios and absolute cross sections have been measured for the dissociative recombination of DCCCN+ and DCCCND+ using the CRYRING ion storage ring. In the case of DCCCN+ the dissociation y ...

Branching ratios and absolute cross sections have been measured for the dissociative recombination of (SO2+)-O-18 using the CRYRING ion storage ring. The branching ratio of the (SO2+)-O-18 + e(-)-->(SO)-O-18+O-18 channel amounts to 61%, while the three-body breakup (SO2+)-O-18 + e(-)-->S+2(18)O accounts for the remaining 39% of the total reaction. The cross section of the reaction could be fitted by the expression sigma=(1.2+/-0.4)x10(-15) E-0.96+/-0.02 cm(2), which leads to a thermal reaction rate of k(T)=(4.6+/-0.2)x10(-7)(T/300 K)(-0.52+/-0.02) cm(3) mol(-1) s(-1).

An investigation into the dissociative recombination process for H(13)CO(+) using merged ion-electron beam methods has been performed at the heavy ion storage ring CRYRING, Stockholm, Sweden. We have measured the branching fractions of the different product channels at ∼ 0 eV collision energy to be the following: CO + H 87 ± 2%, OH + C 9 ± 2%, and O + CH 4 ± 2%. The formation of electronically excited CO in the dominant reaction channel has also been studied, and we report the following tentative branching fractions for the different CO product electronic states: CO(X (1)Σ(+)) + H, 54 ± 10%; CO(a (3)Π) + H, 23 ± 4%; and CO(a' (3)Σ(+)) + H, 23 ± 4%. The absolute cross section between ∼ 2-50 000 meV was measured and showed resonance structures between 3 and 15 eV. The cross section was fitted in the energy range relevant to astrophysics, i.e., between 1 and 300 meV, and was found to follow the expression σ = 1.3 ± 0.3 × 10(-16) E(-1.29 ± 0.05) cm(2) and the corresponding thermal rate constant was determined to be k(T) = 2.0 ± 0.4 × 10(-7)(T/300)(-0.79 ± 0.05) cm(3) s(-1). Radioastronomical observations with the IRAM 30 m telescope of HCO(+) toward the Red Rectangle yielded an upper column density limit of 4 × 10(11) cm(-2) of HCO(+) at the 1σ level in that object, indicating that previous claims that the dissociative recombination of HCO(+) plays an important role in the production of excited CO molecules emitting the observed Cameron bands in that object are not supported.

The fragmentation pattern of the peptide model system, N-methylacetamide, is investigated using ion time-of-flight (TOF) spectroscopy after resonant K-shell excitation. Corresponding near-edge X-ray absorption fine structure (NEXAFS) spectra recorded at high resolution at the C1s, N1s and O1s edges are presented. Analysis of the ion TOF data reveals a multitude of fragmentation channels and dissociation pathways. Comparison between the excitation of six different resonances in the vicinity of the C1s, N1s and O1s edges suggests evidence for site-selective bond breaking. In particular the breaking of the peptide bond and the N-C-alpha bond show a clear correlation with resonant excitation at the N1s edge. Also, stronger tendencies towards site-selective bond breaking are found for the generation of single ions compared with ion pairs. Analysis of angular distributions of ions from breakage of the peptide bond yields a fragmentation time of

We present a study into the collision-induced dissociation (possibly including electron stripping) of O-3(+) and N-3(+) with rest gas molecules (predominantly H-2) in the heavy-ion storage ring CRY ...

Covariance maps of correlated electron emission processes associated with the formation of multiply-ionized core hole states and subsequent decay processes of atoms and molecules upon absorption of x-ray photons from an FEL source are presented.

The dissociative recombination (DR) of CH{sub 5}{sup +} and CD{sub 5}{sup +} has been studied at the heavy-ion storage ring CRYRING. The fragmentation dynamics of the dominant reaction channel CH{sub 3}+H+H has been investigated using an imaging detector. The results indicate that a two-step process via the production of a CH{sub 4} intermediate, which has sufficient energy to fragment further to CH{sub 3}+H, may play an important role. Discrepancies between the present and earlier results obtained from storage ring measurements with those from flowing afterglow experiments are addressed. Newly measured branching fractions in the DR of CD{sub 5}{sup +} show an excellent agreement with branching fractions previously measured for CH{sub 5}{sup +}, and the absolute DR cross sections have been also measured over an interaction energy range between {approx}0 and 0.1 eV for both isotopologs.

We have investigated the dissociative recombination of the N2O+ ion using the CRYRING heavy-ion storage ring at the Manne Siegbahn laboratory in Stockholm, Sweden. The dissociative recombination branching ratios were determined at minimal (approximately 0 eV) collision energy, showing that the dominating pathways involved two-body fragmentation: N2 + O (48%) and NO + N (36%). The branching ratio of the three-body break-up 2N + O was 16%. The overall thermal rate coefficient of the title reaction follows the expression k(T) = 3.34 +/- 0.75 x 10(-7) (T/300) (-0.57+/- 0.03 cm3 s(-1)), which correlates perfectly with earlier flowing afterglow studies on the same process.

Dissociative recombination of BH$_2^+$: the dominance of two-body break-up and an understanding of the fragmentation

The dissociative recombination of fully deuterated protonated acetonitrile, CD(3)CND(+), has been investigated at the CRYRING heavy ion storage ring, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Branching fractions were measured at approximately 0 eV relative collision energy between the ions and the electrons and in 65% of the DR events there was no rupture of bonds between heavy atoms. In the remaining 35%, one of the bonds between the heavy atoms was broken. The DR cross-section was measured between approximately 0 eV and 1 eV relative collision energy. In the energy region between 1 meV and 0.1 eV the cross section data were best fitted by the expression sigma = 7.37 x 10(-16) (E/eV)(-1.23) cm(2), whereas sigma = 4.12 x 10(-16) (E/eV)(-1.46) cm(2) was the best fit for the energy region between 0.1 and 1.0 eV. From the cross section a thermal rate coefficient of alpha(T) = 8.13 x 10(-7) (T/300)(-0.69) cm(3) s(-1) was deduced.

The most up-to-date theoretical calculation on the dissociative recombination (DR) of D2H+ predicts a 2-5 times lower rate coefficient than that obtained experimentally at the Test Storage Ring (TSR). In order to verify the validity either of the experimental results or the theoretical calculations we have studied the DR of D2H+ at the storage ring CRYRING. The rate coefficient has been measured over the interaction energy range from approximate to 0 eV to 50 eV and has been found to have a peak at about 10 eV with a value of 1.6 x 10(-8) cm(3) s(-1), which is in excellent agreement with the result reported from TSR. Taking into account the electron temperature distributions, excellent agreement between the two storage rings measurements is also obtained at smaller interaction energies. The branching fraction analysis has been performed at approximate to 0 eV interaction energy and revealed the following results at the 1 sigma confidence level: N(D+D+H)=76.5%+/-2.2%, N(D-2+H)= 10.0%+/-0.7%, and N(DH+D)=13.5%+/-1.5%. The value of 2N(D-2+H)/N(DH+D)=1.48+/-0.22 implies that formation of D-2 is more favorable than DH.

We report an investigation into the dissociative recombination of the azide radical cation, N(3) (+). The reaction rate constant has been measured to be 6.47 x 10(-7) cm(3) s(-1) at room temperature. This value is smaller than those reported earlier for the ion-electron neutralization of N(3) (+) at nitrogen atmospheric pressure. A strong propensity to dissociate through the N(2)+N channel has been observed.

Dissociative recombination of the deuterated acetaldehyde ion CD3CDO(+) has been studied at the heavy-ion storage ring CRYRING, located at the Manne Siegbahn Laboratory, Stockholm, Sweden. Product branching fractions together with absolute DR cross-sections were measured. The branching fractions were determined at a relative collision energy between the ions and the electrons of approximately 0 eV. With a probability of 34% the DR events resulted in no ruptures of bonds between heavy atoms (i.e. no breakage of the C-C bond or the C[double bond, length as m-dash]O bond). In the remaining 66% of the events one of the bonds between the heavy atoms was broken. The energy-dependent cross-section for the DR reaction was measured between approximately 0 and 1 eV relative kinetic energy. In the energy region between 1 meV and 0.2 eV the absolute cross section could be fitted by the expression sigma(E) = 6.8 x 10(-16)E(-1.28) cm(2), whereas in the energy interval between 0.2 and 1 eV the data were best fitted by sigma(E) = 4.1 x 10(-16)E(-1.60) cm(2). From these cross section data the thermal rate coefficient (as a function of the electron temperature), alpha(T) = 9.2 x 10(-7) (T/300)(-0.72) cm(3) s(-1) was obtained.

Experimental studies of the radiative lifetime of the sole excited state in the nickel anion are presented. Beams of Ni- stored in DESIREE at cryogenic temperatures were subject to photodetachment at different photon energies and the resulting neutrals collected. Preliminary analysis of the decay in neutral production yields a radiative lifetime of approximately 15 seconds for the 3d94s2 2D3/2 excited state.

We have measured the rates of neutrals produced from 10 keV Cn− or CnH− (n=2, 4, 6, 8, and 10) ion beams stored in one of DESIREE's 14 K storage rings. For n=4, 6, and 8 we observe marked differences between Cn− and CnH− cooling rates as inverse internal conversion [cf. S. Martin et al (2013) Phys. Rev. Lett. 110, 063003] processes are effective for the Cn− ions only. Knowledge of the cooling rates of these ions are important for estimates of their formation and destruction rates in cold interstellar environments.

We have measured the spontaneous neutral particle emission from beams of copper cluster anions (Cu−N, N = 3 − 6) stored in an electrostatic storage ring. These experiments have show that multiple structural isomers may be present in the beam.

We have used one of the cryogenic ion storage rings of DESIREE to measure the lifetime of the 2P°1/2 level in the sulfur anion to be 503 ± 43 seconds. This is orders of magnitude longer than any previously measured lifetime in a negatively charged ion.

We have measured the total cross sections and kinetic energy distributions of the neutral fragments for the mutual neutralization of C− and O− with C+, N+ and O+ by using a merged beam apparatus. A fine resolution in the kinetic energy spectra of the product neutral atoms has allowed us to uniquely identify the atomic states which are participating in the mutual neutralization process. A detailed analysis of the branching ratios sheds new light on these charge transfer processes.

International audience; Cross sections and branching ratios are presented for the dissociative recombination of the CF+2 and CF+3 ions with electrons. It is found that the channel producing CF + F is dominant for the reaction with CF+2 and the production of CF2 + F is dominant for the reaction with CF+3. The cross sections for these two ions are very similar.

Here we will briefly describe the commissioning of the Double ElectroStatic Ion Ring ExpEriment (DESIREE) facility at Stockholm University, Sweden. This device uses purely electrostatic focussing and deflection elements and allows ion beams of opposite charge to be confined under extreme high vacuum and cryogenic conditions in separate “rings” and then merged over a common straight section. This apparatus allows for studies of interactions between cations and anions at very low and well-defined centre-of-mass energies (down to a few meV) and at very low internal temperatures (down to a few K).

Covariance mapping is used to investigate electron emission of double core hole states and associated decay processes of atoms and molecules upon absorption of multiple X-ray photons provided by an FEL source.

The dissociative recombination (DR) of N2H+ has been reinvestigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. Thermal rate coefficients for electr ...

Aims. We determine branching fractions, cross sections and thermal rate constants for the dissociative recombination of CD3CDOD + and CH3CH2OH + at the low relative kinetic energies encountered in the interstellar medium. Methods. The experiments were carried out by merging an ion and electron beam at the heavy ion storage ring CRYRING, Stockholm, Sweden. Results. Break-up of the CCO structure into three heavy fragments is not found for either of the ions. Instead the CCO structure is retained in 23 ± 3% of the DR reactions of CD3CDOD + and 7 ± 3% in the DR of CH3CH2OH + , whereas rupture into two heavy fragments occurs in 77 ± 3% and 93 ± 3% of the DR events of the respective ions. The measured cross sections were fitted between 1–200 meV yielding the following thermal rate constants and cross-section dependencies on the relative kinetic energy: σ(Ecm[eV]) = 1.7 ± 0.3 × 10 −15 (Ecm[eV]) −1.23±0.02 cm 2 and k(T) = 1.9 ± 0.4 × 10 −6 (T/300) −0.73±0.02 cm 3 s −1 for CH3CH2OH + as well as k(T) = 1.1 ± 0.4 × 10 −6 (T/300) −0.74±0.05 cm 3 s −1 and σ(Ecm[eV]) = 9.2 ± 4 × 10 −16 (Ecm[eV]) −1.24±0.05 cm 2 for CD3CDOD +

Aims: Determination of branching fractions, cross sections and thermal rate coefficients for the dissociative recombination of CD3OCD2+ (0-0.3 eV) and (CD3)2OD+ (0-0.2 eV) at the low relative kinet ...

The dissociative recombination of the acetaldehyde cation, CH(3)CHO(+), has been investigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. The dependence of the absolute cross section of the reaction on the relative kinetic energy has been determined and a thermal rate coefficient of k(T) = (1.5 ± 0.2) × 10(-6) (T/300)(-0.70±0.02) cm(3) s(-1) has been deduced, which is valid for electron temperatures between ∼10 and 1000 K. The branching fractions of the reaction were studied at ∼0 eV relative kinetic energy and we found that breaking one of the bonds between two of the heavy atoms occurs in 72 ± 2% of the reactions. In the remaining events the three heavy atoms stay in the same product fragment. While the branching fractions are fairly similar to the results from an earlier investigation into the dissociative recombination of the fully deuterated acetaldehyde cation, CD(3)CDO(+), the thermal rate coefficient is somewhat larger for CH(3)CHO(+). Astrochemical implications of the results are discussed.

In the paper we report the first experimental observation of rotational state effects in dissociative recombination of H2+. We also report the branching fractions from the DR of BH2+ N3+ and O3+ and the dynamics occurring in the full fragmentation channel are discussed.

The determination of the dissociative recombination rate coefficient of H(3) (+) has had a turbulent history, but both experiment and theory have recently converged to a common value. Despite this convergence, it has not been clear if there should be a difference between the rate coefficients for ortho-H(3) (+) and para-H(3) (+). A difference has been predicted theoretically and could conceivably impact the ortho:para ratio of H(3) (+) in the diffuse interstellar medium, where H(3) (+) has been widely observed. We present the results of an experiment at the CRYRING ion storage ring in which we investigated the dissociative recombination of highly enriched ( approximately 83.6%) para-H(3) (+) using a supersonic expansion source that produced ions with T(rot) approximately 60-100 K. We observed an increase in the low energy recombination rate coefficient of the enriched para-H(3) (+) by a factor of approximately 1.25 in comparison to H(3) (+) produced from normal H(2) (ortho:para=3:1). The ratio of the rate coefficients of pure para-H(3) (+) to that of pure ortho-H(3) (+) is inferred to be approximately 2 at low collision energies; the corresponding ratio of the thermal rate coefficients is approximately 1.5 at electron temperatures from 60 to 1000 K. We conclude that this difference is unlikely to have an impact on the interstellar ortho:para ratio of H(3) (+).

The dissociative recombination of OPCl+ and OPCl2+ has been studied at the storage ring CRYRING. The rate constants as a function of electron temperature have been derived to be 7.63 x 10(-7)(Te/300)(-0.89) and1.2 x 10(-6)(Te/300)(-1.22) cm3s(-1), respectively. The lower limit quoted for the latter rate constant reflects the experimental inability to detect all of the reaction products. The branching fractions from the reaction have been measured for OPCl+ at approximately 0 eV interaction energy and are determined to be N(O+P+Cl)=(16+/-7)%, N(O+PCl)=(16+/-3)% and N(OP+Cl)=(68+/-5)%. These values have been obtained assuming that the rearrangement channel forming P+ClO is negligible, and ab initio calculations using GAUSSIAN03 are presented for the ion structures and energetics to support such an assumption. Finally, the limitations to using heavy ion storage rings such as CRYRING for studies into the dissociative recombination of large singly charged molecular ions are discussed.

Abstract Radiative cooling of carbon cluster anions C2n+1− (n = 3–5) is investigated using the cryogenic electrostatic ion storage ring DESIREE. Two different strategies are applied to infer infrared emission on slow (milliseconds to seconds) and ultraslow (seconds to minutes) timescales. Initial cooling of the ions over the millisecond timescale is probed indirectly by monitoring the decay in the yield of spontaneous neutralization by thermionic emission. The observed cooling rates are consistent with a statistical model of thermionic electron emission in competition with infrared photon emission due to vibrational de-excitation. Slower cooling over the seconds to minutes timescale associated with infrared emission from low-frequency vibrational modes is probed using time-dependent action spectroscopy. For C9− and C11−, cooling is evidenced by the time-evolution of the yield of photo-induced neutralization following resonant excitation of electronic transitions near the detachment threshold. The cross-section for resonant photo-excitation is at least two orders of magnitude greater than for direct photodetachment. In contrast, C7− lacks electronic transitions near the detachment threshold. Graphical abstract