| 1. |
- Al-Khalili, A, et al.
(författare)
-
Dissociative recombination cross section and branching ratios of protonated dimethyl disulfide and N-methylacetamide
- 2004
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 121:12, s. 5700-5708
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 2. |
- Geppert, W D, et al.
(författare)
-
Dissociative recombination of nitrile ions : DCCCN+ and DCCCND
- 2004
-
Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 613:2, s. 1302-1309
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 3. |
- Geppert, W D, et al.
(författare)
-
Dissociative recombination of (SO2+)-O-18 : Evidence for three-body breakup
- 2004
-
Ingår i: Astrophysical Journal. - : American Astronomical Society. - 0004-637X .- 1538-4357. ; 610:2, s. 1228-1233
-
Tidskriftsartikel (refereegranskat)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).
|
|
| 4. |
- Någård, M. B., et al.
(författare)
-
Dissociative recombination of D+(D2O)(2) water cluster ions with free electrons
- 2002
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 117:11, s. 5264-5270
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 5. |
- Öjekull, Jenny, 1973, et al.
(författare)
-
Dissociative recombination of NH4+ and ND4+ ions : Storage ring experiments and ab initio molecular dynamics
- 2004
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 120:16, s. 7391-7399
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 6. |
- Geppert, W D, et al.
(författare)
-
Dissociative recombination of C3H4+ : preferential formation of the C3H3 radical
- 2004
-
Ingår i: International Journal of Mass Spectrometry. - : Elsevier BV. - 1387-3806 .- 1873-2798. ; 237:1, s. 25-32
-
Tidskriftsartikel (refereegranskat)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).
|
|
| 7. |
- Geppert, W D, et al.
(författare)
-
Dissociative recombination of N2OD
- 2004
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 6:13, s. 3415-3419
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 8. |
- Geppert, W D, et al.
(författare)
-
Extraordinary branching ratios in astrophysically important dissociative recombination reactions
- 2004
-
Ingår i: Faraday discussions. - : Royal Society of Chemistry (RSC). - 1359-6640 .- 1364-5498. ; 127, s. 425-437
-
Tidskriftsartikel (refereegranskat)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.
|
|
| 9. |
|
|
