| 1. |
- Al-Khalili, A, et al.
(author)
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Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide
- 2004
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 121:12, s. 5700-5708
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Journal article (peer-reviewed)abstract
- Dimethyl disulfide (DMDS) and N-methylacetamide are two first choice model systems that represent the disulfide bridge bonding and the peptide bonding in proteins. These molecules are therefore suitable for investigation of the mechanisms involved when proteins fragment under electron capture dissociation (ECD). The dissociative recombination cross sections for both protonated DMDS and protonated N-methylacetamide were determined at electron energies ranging from 0.001 to 0.3 eV. Also, the branching ratios at 0 eV center-of-mass collision energy were determined. The present results give support for the indirect mechanism of ECD, where free hydrogen atoms produced in the initial fragmentation step induce further decomposition. We suggest that both indirect and direct dissociations play a role in ECD.
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| 2. |
- Geppert, W D, et al.
(author)
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Dissociative recombination of nitrile ions : DCCCN+ and DCCCND
- 2004
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In: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 613:2, s. 1302-1309
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Journal article (peer-reviewed)abstract
- 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 yielding D + C3N and those leading to two fragments containing a pair of heavy atoms dominate, whereas pathways producing a fragment with three heavy atoms play only a minor role. Conversely, for DCCCND+, only those channels preserving the carbon chain or producing two fragments with a pair of heavy atoms each are detected. The cross sections of the reactions are very similar and can be fitted to the expressions sigma = (2.9 +/- 0.5) x 10(-15)E(eV)(-1.05 +/- 0.02) cm(2) and sigma = (2.3 +/- 0.4) x 10(-15)E(eV)(-1.10 +/- 0.02) cm(2) for DCCCN+ and DCCCND+, respectively. From these data, thermal reaction rates of k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.60 +/- 0.02) cm(3) s(-1) and k(T) = (1.5 +/- 0.3) x 10(-6)(T/300 K)(-0.58 +/- 0.02) cm(3) s(-1) were calculated for DCCCN+ and DCCCND+, respectively. These rates and branching ratios are compared with those hitherto used in astrophysical models.
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| 3. |
- Geppert, W. D., et al.
(author)
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Dissociative recombination of N2H+ : Evidence for fracture of the N-N bond
- 2004
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In: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 609:1, s. 459-464
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Journal article (peer-reviewed)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2H+ using the CRYRING ion storage ring. It has been found that the channel N2H+ + e(-) --> N-2 + H accounts for only 36% of the total reaction and that the branching into the other exoergic pathway, N2H+ + e(-) --> NH + N, consequently amounts to 64%. The cross section of the reaction could be fitted by the expression sigma = (2.4 +/- 0.4) x 10(-16) E-1.04 +/- 0.02 cm(2), which leads to a thermal reaction rate of k(T) = (1.0 +/- 0.2) x 10(-7)(T/300)(-0.51 +/- 0.02) cm(3) s(-1), in favorable agreement with previous flowing afterglow Langmuir probe measurements at room temperature, although our temperature dependence is very different. The implications of these measurements for the chemistry of interstellar clouds are discussed. A standard model calculation for a dark cloud predicts a slight increase of N2H+ in the dark clouds but a five- to sevenfold increase of the NH concentration as steady state is reached.
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| 4. |
- Geppert, W D, et al.
(author)
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Dissociative recombination of (SO2+)-O-18 : Evidence for three-body breakup
- 2004
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In: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 610:2, s. 1228-1233
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Journal article (peer-reviewed)abstract
- 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).
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| 5. |
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| 6. |
- Någård, M. B., et al.
(author)
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Dissociative recombination of D+(D2O)(2) water cluster ions with free electrons
- 2002
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 117:11, s. 5264-5270
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Journal article (peer-reviewed)abstract
- Dissociative recombination (DR) of the water cluster ion D+(D2O)(2) has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). Cluster ions were injected into the ring and accelerated to an energy of 2.28 MeV. The stored ion beam was merged with an almost monoenergetic electron beam, and neutral fragments produced by DR were detected by an energy-sensitive surface barrier detector. The first experimental determinations of the absolute DR cross section and branching ratios for a cluster ion are reported. The cross section for the process D+(D2O)(2)+e(-) is large and reaches 6.10(-12) cm(2) at a low center-of-mass collision energy of 0.001 eV. The cross section has an E-1.19+/-0.02 dependence in the energy range 0.001-0.0052 eV, and a steeper slope with an E-1.70+/-0.12 dependence for E=0.052-0.324 eV. The general trends are similar to the results for previously studied molecular ions, but the cross section is higher in absolute numbers for the cluster ion. Thermal rate coefficients for electron temperatures of 50-2000 K are deduced from the cross section data and the rate coefficients are consequently also large. Branching ratios for the product channels are determined with a grid technique. Break-up into 2D(2)O+D is the dominating dissociation channel with a probability of 0.94+/-0.04. The channel resulting in the fragments D2O+OD+D-2 has a probability of 0.04+/-0.02, and the probability for formation of D3O+D2O is 0.02+/-0.03. The results are compared with data for molecular ions, and the cluster dissociation dynamics are discussed.
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| 7. |
- Zhaunerchyk, V, et al.
(author)
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Dissociative recombination study of Na+(D2O) in a storage ring
- 2004
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 121:21, s. 10483-10488
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Journal article (peer-reviewed)abstract
- The dissociative recombination of Na+(D2O) ion has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The cross section has been measured as a function of center-of-mass energy ranging from 1 meV to 0.1 eV and found to have an E-1.37 dependence. The rate coefficient has been deduced to be (2.3+/-0.32)x10(-7)(T-e/300)(-0.95+/-0.01) cm(3) s(-1) for T-e=50-1000 K. The branching ratios have been measured at 0 eV. Of the four energetically accessible dissociation channels, three channels are found to occur although the channel that breaks the weak Na+-D2O bond is by far dominant.
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| 8. |
- Ellmann, A, et al.
(author)
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Radiative lifetime of a bound excited state of Te-
- 2004
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In: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 92:25, s. 253002-
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Journal article (peer-reviewed)abstract
- We report on the first experimental study of the lifetime of a bound excited state of a negative ion. A new experimental technique was developed and used to measure the radiative lifetime of the 5p(5) P-2(1/2) level of Te-. The experiment was performed in a magnetic storage ring, where a laser beam was applied along one of the straight sections. In the experiment the population of the excited J=1/2 level was probed each time the Te- ions passed through the laser field. A decay curve was built up by sampling the population of the excited level of the Te- ions as a function of time after injection into the ring. A multiconfiguration Dirac-Hartree-Fock calculation was performed in conjunction with the experiment. The calculation yielded a radiative lifetime of 0.45 s, in excellent agreement with the measured value of 0.42(5) s.
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| 9. |
- Fritioff, Karin, et al.
(author)
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Observation of an excited C2-4 ion
- 2004
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In: Journal of Physics B: Atomic, Molecular and Optical Physics. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 37:11, s. 2241-2246
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Journal article (peer-reviewed)abstract
- This paper reports an experimental investigation of the electron impact detachment of C−4. We observe structure in the electron impact cross section for detaching a single electron from a C−4 cluster anion, which we attribute to the formation and decay of the C2−4 dianion. The system is energetically unstable and very rapidly decays via double autodetachment. The energy and width of the resonance were determined to be 8.8(5) eV and 1.4(5) eV, respectively, and the resonance lies 1.5(5) eV above the ground state of the neutral system. The experiment was conducted by merging monoenergetic electron and ion beams in the heavy ion storage ring CRYRING. The detachment channel was monitored by detecting neutral C4 fragments.
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| 10. |
- Geppert, W D, et al.
(author)
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Extraordinary branching ratios in astrophysically important dissociative recombination reactions
- 2004
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In: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 127, s. 425-437
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Journal article (peer-reviewed)abstract
- Branching ratios of the dissociative recombination reactions of the astrophysically relevant ions DCO+, N2H+ and DOCO+ ( as substitute for HOCO+) have been measured using the CRYRING storage ring at the Manne Siegbahn Laboratory at the University of Stockholm, Sweden. For DCO+, the channel leading to D and CO was by far the most important one ( branching ratio 0.88), only small contributions of the CD+O and OD+C product pathways ( branching ratios 0.06 each) were recorded. In the case of N2H+ the surprising result of a break-up of the N-N bond to N and NH ( branching ratio 0.64) was found with the branching ratio of the N-2+H product channel therefore displaying a branching ratio of only 0.36. In the case of DOCO+, the three-body break-up into D+O+CO dominated ( branching ratio 0.68), whereas the contribution of the CO2+H channel was only minute (0.05). The remaining share ( branching ratio 0.27) was taken by the pathway leading to OH+CO. For the dissociative recombination of N2H+ and DOCO+ also absolute reaction cross sections were obtained in the collisional energy range between 0 and 1 eV. From these cross sections it was possible to work out the thermal rate constants, which were found to be k(T) = 1.0 +/- 0.1 x 10(-7) (T/300 K)(-0.51 +/- 0.02) cm(3) s(-1) and k(T) = 1.2 +/- 0.1 x 10(-6) (T/300 K)(-0.64 +/- 0.02) cm(3) s(-1) for N2H+ and DOCO+, respectively.
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| 11. |
- Öjekull, Jenny, 1973, et al.
(author)
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Dissociative recombination of NH4+ and ND4+ ions : Storage ring experiments and ab initio molecular dynamics
- 2004
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In: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 120:16, s. 7391-7399
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Journal article (peer-reviewed)abstract
- The dissociative recombination (DR) process of NH4+ and ND4+ molecular ions with free electrons has been studied at the heavy-ion storage ring CRYRING (Manne Siegbahn Laboratory, Stockholm University). The absolute cross sections for DR of NH4+ and ND4+ in the collision energy range 0.001-1 eV are reported, and thermal rate coefficients for the temperature interval from 10 to 2000 K are calculated from the experimental data. The absolute cross section for NH4+ agrees well with earlier work and is about a factor of 2 larger than the cross section for ND4+. The dissociative recombination of NH4+ is dominated by the product channels NH3+H (0.85+/-0.04) and NH2+2H (0.13+/-0.01), while the DR of ND4+ mainly results in ND3+D (0.94+/-0.03). Ab initio direct dynamics simulations, based on the assumption that the dissociation dynamics is governed by the neutral ground-state potential energy surface, suggest that the primary product formed in the DR process is NH3+H. The ejection of the H atom is direct and leaves the NH3 molecule highly vibrationally excited. A fraction of the excited ammonia molecules may subsequently undergo secondary fragmentation forming NH2+H. It is concluded that the model results are consistent with gross features of the experimental results, including the sensitivity of the branching ratio for the three-body channel NH2+2H to isotopic exchange.
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| 12. |
- Balthasar, Michael, et al.
(author)
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Detailed Modeling of soot formation in a partially stirred plug flow reactor
- 2002
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In: Combustion and Flame. - 0010-2180. ; 128:4, s. 395-409
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Journal article (peer-reviewed)abstract
- The purpose of this work is to propose a detailed model for the formation of soot in turbulent reacting flow and to use this model to study a carbon black furnace. The model is based on a combination of a detailed reaction mechanism to calculate the gas phase chemistry, a detailed kinetic soot model based on the method of moments, and the joint composition probability density function (PDF) of these scalar quantities. Two problems, which arise when modeling the formation of soot in turbulent flows using a PDF approach, are studied. A consistency study of the combined scalar-soot moment approach reveals that the molecular diffusion term in the PDF-equation can be closed by the IEM and Curl-type mixing models. An investigation of different kernels for the collision frequency of soot particles shows that the influence of turbulence on particle coagulation is negligible for typical flame conditions and the particle size range considered. The model is used as a simple toot to simulate a furnace black process, which is the most important industrial process for the production of carbon blacks. Despite the simplifications in the modeling of the turbulent flow reasonable agreement between the calculated soot yield and data measured in an industrial furnace black reactor is achieved although no adjustments were made to the kinetic parameters of the soot model. The effect of the mixing intensity on soot yield and different soot formation rates is investigated. In addition the influence of different operating conditions such as temperature and equivalence ratio in the primary zone of the reactor is studied.
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| 13. |
- Balthasar, Michael, et al.
(author)
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Implementation and validation of a new soot model and application to aeroengine combustors
- 2002
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In: Journal of Engineering for Gas Turbines and Power. - : ASME International. - 1528-8919 .- 0742-4795. ; 124:1, s. 66-74
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Journal article (peer-reviewed)abstract
- The modeling of soot formation and oxidation under industrially relevant conditions has made significant progress in recent years. Simplified models introducing a small number of transport equations into a CFD Code have been used with some success in research configurations simulating a reciprocating diesel engine. Soot formation and oxidation in the turbulent flow is calculated on the basis of a laminar flamelet library model. The gas phase reactions are modeled with a detailed mechanism for the combustion of heptane containing 89 species and 855 reactions developed by Frenklach and Warnatz and revised by Mauss. The soot model is divided into gas phase reactions. the growth of polycyclic aromatic hydrocarbons (PAH) and the processes of particle inception, heterogeneous face growth, oxidation, and condensation. The first two are modeled within the laminar flamelet chemistry, while the soot model deals with the soot particle processes. The time scales of soot formation are assumed to he much larger than the turbulent time scales. Therefore rates of soot formation are tabulated in the flamelet libraries rather than the soot volume fraction itself. The different rates of soot formation, e.g., particle inception, sinface growth, firagmentation, and oxidation, computed on the basis of a detailed soot model, are calculated in the dissipation rate space and further simplified by fitting them to simple analytical functions. A transport equation for the mean soot mass fraction is solved in the CFD code. The mean rate in this transport equation is closed with the help of presumed probability density functions for the mixture fraction and the scalar dissipation rate. Heat loss due to radiation can be taken into account by including a heat loss parameter it? the flamelet calculations describing the change of enthalpy due to radiation, but was not used for the results reported here. The soot model was integrated into an existing commercial CFD code is a post-processing module to existing combustion CFD flow fields and is very robust with high convergence rates. The model is validated with laboratory flame data and using a realistic three-dimensional BM V Rolls-Royce combustor configuration, where test data at high pressure are available. Good agreement between experiment and simulation is achieved for laboratory flames, whereas soot is overpredicted for the aeroengine combustor configuration by 1-2 orders of magnitude.
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| 14. |
- Behave, A, et al.
(author)
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Analysis of a natural gas fuelled homogeneous charge compression ignition engine with exhaust gas recirculation using a stochastic reactor model
- 2004
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In: International Journal of Engine Research. - : SAGE Publications. - 1468-0874 .- 2041-3149. ; 5, s. 93-104
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Journal article (peer-reviewed)abstract
- Combustion and emissions formation in a Volvo TD 100 series diesel engine running in a homogeneous charge compression ignition (HCCI) mode and fuelled with natural gas is simulated and compared with measurements for both with and without external exhaust gas recirculation (EGR). A new stochastic approach is introduced to model the convective heat transfer, which accounts for fluctuations and fluid-wall interaction effects. This model is included in a partially stirred plug flow reactor (PaSPFR) approach, a stochastic reactor model (SRM), and is applied to study the effect of EGR on pressure, autoignition timing and emissions of CO and unburned hydrocarbons (HCs). The model accounts for temperature inhomogeneities and includes a detailed chemical mechanism to simulate the chemical reactions within the combustion chamber. Turbulent mixing is described by the interaction by exchange with the mean (IEM) model. A Monte Carlo method with a second-order time-splitting technique is employed to obtain the numerical solution. The model is validated by comparing the simulated in-cylinder pressure history and emissions with measurements taken from Christensen and Johansson (SAE Paper 982454). Excellent agreement is obtained between the peak pressure, ignition timing and CO and HC emissions predicted by the model and those obtained from the measurements for the non-EGR, 38 per cent EGR and 47 per cent EGR cases. A comparison between the pressure profiles for the cases studied reveals that the ignition timing and the peak pressure are dependent on the EGR. With EGR, the peak pressure reduces and the autoignition is delayed. The trend observed in the measured emissions with varying EGR is also predicted correctly by the model.
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| 15. |
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| 16. |
- Fritioff, K, et al.
(author)
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Single and double detachment from H-
- 2004
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In: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622 .- 2469-9926 .- 2469-9934. ; 69:4, s. 042707-
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Journal article (peer-reviewed)abstract
- Absolute cross sections for single and double detachment from H- following electron impact have been measured over a range of collision energies from the thresholds to 170 eV. The measurements were made using a magnetic storage ring. The ions in the ring were merged with a monoenergetic electron beam and neutral and positively charged fragments were detected. We cover larger energy ranges than in many of the previous experiments, and this is the first time both single and double detachment have been measured simultaneously. This allows us to present accurate ratios between the single and double detachment cross sections. On the basis of these ratio measurements we discuss possible mechanisms leading to double detachment.
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| 17. |
- Geppert, W D, et al.
(author)
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Dissociative recombination of C3H4+ : preferential formation of the C3H3 radical
- 2004
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In: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806 .- 1873-2798. ; 237:1, s. 25-32
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Journal article (peer-reviewed)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of C3H4+ using the CRYRING ion storage ring. The pre-eminent channel involves the production of C3H3 and H, whereas processes involving rupture of carbon-carbon bonds are clearly disfavoured. The cross section of the reaction could be fitted to the expression sigma = 5.5 +/- 0.2 x 10(-15) E-1.01+/-0.02, which leads to a thermal reaction rate of k(T) = 2.95 +/- 0.1 x 10(-6) (T/300)(-0.67+/-0.02) cm(3) s(-1).
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| 18. |
- Geppert, W D, et al.
(author)
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Dissociative recombination of N2OD
- 2004
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In: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 6:13, s. 3415-3419
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Journal article (peer-reviewed)abstract
- Branching ratios and absolute cross sections have been measured for the dissociative recombination of N2OD+ using the CRYRING ion storage ring. The most dominating pathways were found to be those eading to N-2 + OD (46%) and the three-body break-up producing N-2 + O + D (40%). The production of N2O is not observed. The cross section of the reaction could be fitted to the expression sigma = 1.25 +/- 0.25 x 10(-15)(E/eV)(-1.24+/-0.02), which leads to a thermal reaction rate of k(T) = 1.4 +/- 0.1 x 10(-6)(T/300)(-0.74+/-0.02) cm(3) s(-1). The findings are compared with those of the related dissociative recombination of DOCO+ as well as with earlier flowing afterglow measurements.
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| 19. |
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