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Mutual neutralisation reactions in planetary atmospheres and industrial plasmas
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0003-4515-9691
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with experimental studies of electron transfer reactions between oppositely charged ions (cations and anions), in a process called mutual neutralisation. These investigations were performed at the double electrostatic ion storage ring DESIREE at Stockholm University, which was put into full operation in 2017. This unique apparatus consists of two cryogenic electrostatic rings where oppositely charged ion beams are stored and merged in a common section where the reactions of interest take place. The neutral products arising from the reactions are detected in coincidence using a sensitive 3D imaging detector. This approach allows the kinetic energy of the products to be measured, and the particular product channels to be identified, such that the branching ratio into the different competing sets of products can be determined. 

The reactions studied in this thesis take place in both natural plasmas, such as our own atmosphere, as well as industrial ones, such as ion propulsion engines and fusion reactors. For the first time, the final-state distribution of the products in a number of mutual neutralisation reactions involving molecular ions were determined, and the reaction dynamics were elucidated. 

The work presented in this thesis deals with the development of data analysis methods necessary for the imaging of coincidence products, as well as simulation methods required to interpret the experimental results. The thesis touches briefly the current theoretical models treating these reactions and their current recent development and results. 

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University , 2024. , p. 90
Keywords [en]
merged ion beams, atmospheric reactions, mutual neutralisation, industrial plasmas, multi particle imaging
National Category
Atom and Molecular Physics and Optics
Research subject
Physics
Identifiers
URN: urn:nbn:se:su:diva-233776ISBN: 978-91-8014-947-1 (print)ISBN: 978-91-8014-948-8 (electronic)OAI: oai:DiVA.org:su-233776DiVA, id: diva2:1900952
Public defence
2024-11-08, FB53, AlbaNova, Roslagstullsbacken 21, and online via Zoom, public link is available at the department website, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2024-10-16 Created: 2024-09-25 Last updated: 2024-10-10Bibliographically approved
List of papers
1. Mutual neutralisation of O+ with O: investigation of the role of metastable ions in a combined experimental and theoretical study
Open this publication in new window or tab >>Mutual neutralisation of O+ with O: investigation of the role of metastable ions in a combined experimental and theoretical study
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2021 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 23, no 43, p. 24607-24616Article in journal (Refereed) Published
Abstract [en]

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.

National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-211321 (URN)10.1039/d1cp03977f (DOI)
Funder
Knut and Alice Wallenberg Foundation, 2018.0028Swedish Research Council, 2017-00621Swedish Research Council, 2018-04092Swedish Research Council, 2019-04379Swedish Research Council, 2020-03404Swedish Research Council, 2020-03437
Available from: 2022-11-17 Created: 2022-11-17 Last updated: 2024-10-31Bibliographically approved
2. Storage-ring study of the mutual neutralization of N+ with O
Open this publication in new window or tab >>Storage-ring study of the mutual neutralization of N+ with O
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2022 (English)In: Physical Review A: covering atomic, molecular, and optical physics and quantum information, ISSN 2469-9926, E-ISSN 2469-9934, Vol. 105, no 6, article id 062825Article in journal (Refereed) Published
Abstract [en]

The double ion storage ring DESIREE has been used in combination with position- and time-sensitive detectors to study the mutual neutralization of N+ with O at 40 meV collision energy. Several previously unassigned spectral features observed in a recent single-pass merged-beams experiment at 7 meV collision energy [Phys. Rev. Lett. 121, 083401 (2018)], were also observed in the present experiment. It was found that neutralization channels of the first metastable state of the cation [N+(1D),τ≈256s] could explain the majority of these features, while the second metastable state [N+(1S),τ≈0.9s] was not found to contribute significantly. The branching ratios into the different electronically excited states of N were determined and found to be in good agreement between the two experiments. Theoretical calculations using the multichannel Landau-Zener model were found to yield good results for a number of channels, but could not describe some observed contributions, possibly due to the presence of other processes not accounted for in the model.

National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-211322 (URN)10.1103/physreva.105.062825 (DOI)000829758500002 ()2-s2.0-85133320356 (Scopus ID)
Funder
Swedish Research Council, 2020-05467Swedish Research Council, 2018-04092,Swedish Research Council, 2020-03404
Available from: 2022-11-17 Created: 2022-11-17 Last updated: 2024-10-31Bibliographically approved
3. Final-state-resolved mutual neutralization in I+ - I collisions
Open this publication in new window or tab >>Final-state-resolved mutual neutralization in I+ - I collisions
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2022 (English)In: Physical Review A: covering atomic, molecular, and optical physics and quantum information, ISSN 2469-9926, E-ISSN 2469-9934, Vol. 106, no 1, article id 012812Article in journal (Refereed) Published
Abstract [en]

We have studied the mutual neutralization reaction of atomic iodine ions (i.e., I++I→I+I) in a cryogenic double electrostatic ion-beam storage-ring apparatus. Our results show that the reaction forms iodine atoms either in the ground-state configuration (I(5p52P∘), ∼40%) or with one atom in an electronically excited state (I(6s2[2]), ∼60%), with no significant variation over the branching ratios in the studied collision-energy range (0.1–0.8 eV). We estimate the total charge-transfer cross section to be of the order of 10−13cm2 at 0.1 eV collision energy. Ab initio relativistic electronic structure calculations of the potential-energy curves of I2 suggest that the reaction takes place at short internuclear distances. The results are discussed in view of their importance for applications in electric thrusters.

National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-211323 (URN)10.1103/physreva.106.012812 (DOI)000832522600012 ()2-s2.0-85135620489 (Scopus ID)
Funder
Swedish Research Council, 2017-00621Swedish Research Council, 2021-00155Knut and Alice Wallenberg Foundation, 2018.0028Knut and Alice Wallenberg Foundation, 2018-04092Knut and Alice Wallenberg Foundation, 2020-03437
Available from: 2022-11-17 Created: 2022-11-17 Last updated: 2024-10-31Bibliographically approved
4. Mutual Neutralization of NO plus with O-
Open this publication in new window or tab >>Mutual Neutralization of NO plus with O-
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2024 (English)In: Physical Review Letters, ISSN 0031-9007, E-ISSN 1079-7114, Vol. 132, no 2, article id 023001Article, review/survey (Refereed) Published
Abstract [en]

We have studied the mutual neutralization reaction of vibronically cold NO+ with O- at a collision energy of approximate to 0.1 eV and under single-collision conditions. The reaction is completely dominated by production of three ground-state atomic fragments. We employ product-momentum analysis in the framework of a simple model, which assumes the anion acts only as an electron donor and the product neutral molecule acts as a free rotor, to conclude that the process occurs in a two-step mechanism via an intermediate Rydberg state of NO which subsequently fragments.

National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-228987 (URN)10.1103/PhysRevLett.132.023001 (DOI)001185794500009 ()38277613 (PubMedID)2-s2.0-85182266242 (Scopus ID)
Available from: 2024-05-08 Created: 2024-05-08 Last updated: 2024-09-25Bibliographically approved
5. Disentangling vibrationally-dependent molecular dynamics in mutual neutralisation reactions
Open this publication in new window or tab >>Disentangling vibrationally-dependent molecular dynamics in mutual neutralisation reactions
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(English)Manuscript (preprint) (Other academic)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-233762 (URN)
Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2024-09-25
6. H2+ + H: the first molecular ion mutual neutralisation reaction in a hydrogen plasma
Open this publication in new window or tab >>H2+ + H: the first molecular ion mutual neutralisation reaction in a hydrogen plasma
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(English)Manuscript (preprint) (Other academic)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-233763 (URN)
Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2024-09-25
7. Disentangling competing dissociative and non-dissociative reaction dynamics in molecular mutual neutralisation reactions
Open this publication in new window or tab >>Disentangling competing dissociative and non-dissociative reaction dynamics in molecular mutual neutralisation reactions
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(English)Manuscript (preprint) (Other academic)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-233768 (URN)
Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2024-09-25
8. Mutual neutralisation of I2+ with I-
Open this publication in new window or tab >>Mutual neutralisation of I2+ with I-
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(English)Manuscript (preprint) (Other academic)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-233769 (URN)
Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2024-09-25
9. The mutual neutralization of hydronium and hydroxide
Open this publication in new window or tab >>The mutual neutralization of hydronium and hydroxide
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2024 (English)In: Science, ISSN 0036-8075, E-ISSN 1095-9203, Vol. 383, no 6680, p. 285-289Article in journal (Refereed) Published
Abstract [en]

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. 

National Category
Physical Chemistry
Identifiers
urn:nbn:se:su:diva-229270 (URN)10.1126/science.adk1950 (DOI)001184776500025 ()38236956 (PubMedID)2-s2.0-85182867022 (Scopus ID)
Available from: 2024-05-23 Created: 2024-05-23 Last updated: 2024-09-25Bibliographically approved
10. Elucidating the role of a molecular anion in mutual neutralisation reactions
Open this publication in new window or tab >>Elucidating the role of a molecular anion in mutual neutralisation reactions
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(English)Manuscript (preprint) (Other academic)
National Category
Atom and Molecular Physics and Optics
Identifiers
urn:nbn:se:su:diva-233771 (URN)
Available from: 2024-09-25 Created: 2024-09-25 Last updated: 2024-09-25

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