Please use this identifier to cite or link to this item:
http://dx.doi.org/10.25673/115387
Title: | Rydberg electron stabilizes the charge localized state of the diamine cation |
Author(s): | Reimann, Marc Kirsch, Christoph Sebastiani, Daniel ![]() Kaupp, Martin |
Issue Date: | 2024 |
Type: | Article |
Language: | English |
Abstract: | A previous controversial discussion regarding the interpretation of Rydberg spectra of gaseous dimethylpiperazine (DMP) as showing the co-existence of a localized and delocalized mixed-valent DMP+ radical cation is revisited. Here we show by high-level quantum-chemical calculations that an apparent barrier separating localized and delocalized DMP+ minima in previous multi-reference configuration-interaction (MRCI) calculations and in some other previous computations were due to unphysical curve crossings of the reference wave functions. These discontinuities on the surface are removed in state-averaged MRCI calculations and with some other, orthogonal high-level approaches, which do not provide a barrier and thus no localized minimum. We then proceed to show that in the actually observed Rydberg state of neutral DMP the 3s-type Rydberg electron binds more strongly to a localized positive charge distribution, generating a localized DMP* Rydberg-state minimum, which is absent for the DMP+ cation. This work presents a case where interactions of a Rydberg electron with the underlying cationic core alter molecular structure in a fundamental way. |
URI: | https://opendata.uni-halle.de//handle/1981185920/117341 http://dx.doi.org/10.25673/115387 |
Open Access: | ![]() |
License: | ![]() |
Journal Title: | Nature Communications |
Publisher: | Nature Publishing Group UK |
Publisher Place: | [London] |
Volume: | 15 |
Issue: | 1 |
Original Publication: | 10.1038/s41467-023-44526-y |
Appears in Collections: | Open Access Publikationen der MLU |
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s41467-023-44526-y.pdf | 626.55 kB | Adobe PDF | ![]() View/Open |