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Charge-Transfer-Induced Predissociation in Rydberg States of Molecular Cations: MgAr.
| Content Provider | Europe PMC |
|---|---|
| Author | Wehrli, Dominik Génévriez, Matthieu Knecht, Stefan Reiher, Markus Merkt, Frédéric |
| Copyright Year | 2021 |
| Abstract | Very little is known about the Rydbergstates of molecular cations,i.e., Rydberg states having a doubly charged ion core. With the exampleof MgAr+, we present general features of the structureand dynamics of the Rydberg states of molecular cations, which wefind are subject to the process of charge-transfer-induced predissociation.Our study focuses on the spectrum of low-n Rydbergstates with potential-energy functions associated with the Mg+(3d and 4s) + Ar(1S0) dissociation asymptotes.In particular, we have recorded spectra of the 3dπΩ′ (Ω′ = 1/2, 3/2) Rydberg states, extending from the lowest (v′ = 0) vibrational levels to their dissociation limits. Thisspectral range encompasses the region where the onset of predissociationby interaction with the mostly repulsive 2Σ and 2Π charge-transfer states associated with the Mg(3s2) + Ar+(2P1/2,3/2) dissociationasymptotes is observed. This interaction leads to very strong perturbationsof the 3dπ Rydberg states of MgAr+, revealed by vibrationalprogressions exhibiting large and rapid variations of the vibrationalintervals, line widths, and spin–orbit splittings. We attributethe anomalous sign and magnitude of the spin–orbit couplingconstant of the 3dπ state to the interaction with a 2Π Rydberg state correlating to the Mg+(4p) + Ar(1S0) dissociation limit. To analyze our spectraand elucidate the underlying process of charge-transfer-induced predissociation,we implemented a model that allowed us to derive the potential-energyfunctions of the charge-transfer states and to quantitatively reproducethe experimental results. This analysis characterizes the main featuresof the dynamics of the Rydberg series converging to the ground stateof MgAr2+. We expect that the results and analysis reportedhere are qualitatively valid for a broader range of singly chargedmolecular cations, which are inherently prone to charge-transfer interactions. |
| Related Links | https://europepmc.org/backend/ptpmcrender.fcgi?accid=PMC8775275&blobtype=pdf |
| ISSN | 10895639 |
| Journal | The Journal of Physical Chemistry. a [J Phys Chem A] |
| Volume Number | 125 |
| DOI | 10.1021/acs.jpca.1c03859 |
| PubMed Central reference number | PMC8775275 |
| Issue Number | 31 |
| PubMed reference number | 34319723 |
| e-ISSN | 15205215 |
| Language | English |
| Publisher | American ChemicalSociety |
| Publisher Date | 2021-07-28 |
| Access Restriction | Open |
| Rights License | Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/). © 2021 American Chemical Society |
| Content Type | Text |
| Resource Type | Article |
| Subject | Medicine Physical and Theoretical Chemistry |
