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Treatment of asymptotic non-adiabatic couplings with higher order reprojection method in the diabatic representation 
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0003-4138-4015
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-4291-2636
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-8532-8130
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2024 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 161, no 5, article id 054303Article in journal (Refereed) Published
Abstract [en]

The problem of asymptotic non-adiabatic couplings in heavy particle collisions is treated using the reprojection method. The mixing matrix that mixes the asymptotic solutions of the coupled states to obtain appropriate boundary conditions is here derived to second order, yielding a faster convergence of the cross section. In addition, the reprojection method is implemented in a diabatic representation and applied to inelastic scattering of Li + Na and H + H collisions and to mutual neutralization in H+ + H collisions.

Place, publisher, year, edition, pages
2024. Vol. 161, no 5, article id 054303
Keywords [en]
reprojection method, asymptotic non-adiabatic couplings
National Category
Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-228797DOI: 10.1063/5.0213714ISI: 001282667900003PubMedID: 39087541Scopus ID: 2-s2.0-85200292204OAI: oai:DiVA.org:su-228797DiVA, id: diva2:1854934
Available from: 2024-04-29 Created: 2024-04-29 Last updated: 2025-01-27Bibliographically approved
In thesis
1. A unified model of reactive scattering processes: Application to the H2 reaction complex
Open this publication in new window or tab >>A unified model of reactive scattering processes: Application to the H2 reaction complex
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, reactive scattering processes involving the H2 reaction complex are studied ab initio and fully quantum mechanically. These processes have in common that they involve highly excited electronic states, which could be either bound or resonant. Non-adiabatic couplings, which can be significant both at small and large internuclear distances, need to be included to account for the interaction between the bound electronic states. In addition, the electronic resonant states interact with the ionization continuum at small internuclear distances, which may cause the collision complex to autoionize. In this work, a model is developed which incorporates these different coupling mechanisms. By introducing a quasidiabatic model at small internuclear distances, resonant states and couplings to the ionization continuum are incorporated. The quasidiabatic model is combined with a strict diabatic description, which rigorously incorporates non-adiabatic couplings among the bound electronic states. Nuclear dynamics are solved for using a close-coupling approach in a strict diabatic representation, where a non-local complex potential is included to account for loss into the ionization continuum. With this model, various reactive scattering processes can systematically be studied using the same set of potential energy curves and couplings. The model is applied in studies of H++H- mutual neutralization, H(1s)+H(ns) and H++H- associative ionization as well as dissociative recombination and resonant ion-pair formation in electron collisions with HD+. Cross sections and branching ratios are compared with results from previous experiments and theoretical studies.

Place, publisher, year, edition, pages
Stockholm: Department of Physics, Stockholm University, 2024. p. 76
Keywords
associative ionization, dissociative recombination, mutual neutralization, resonant ion-pair formation, non-adiabatic dynamics
National Category
Atom and Molecular Physics and Optics
Research subject
Theoretical Physics
Identifiers
urn:nbn:se:su:diva-228804 (URN)978-91-8014-823-8 (ISBN)978-91-8014-824-5 (ISBN)
Public defence
2024-08-23, sal FB42, AlbaNova universitetscentrum, Roslagstullsbacken 21, Stockholm, 13:00 (English)
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Available from: 2024-05-30 Created: 2024-04-29 Last updated: 2024-05-22Bibliographically approved

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Hedvall, PatrikHörnquist, JohanElander, Nils O.Larson, Åsa

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