Rydberg electron stabilizes the charge localized state of the diamine cation

Marc Reimann, Christoph Kirsch, Daniel Sebastiani and Martin Kaupp ()
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Marc Reimann: Technische Universität Berlin
Christoph Kirsch: Martin-Luther-University Halle-Wittenberg
Daniel Sebastiani: Martin-Luther-University Halle-Wittenberg
Martin Kaupp: Technische Universität Berlin

Nature Communications, 2024, vol. 15, issue 1, 1-7

Abstract: 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.

Date: 2024
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DOI: 10.1038/s41467-023-44526-y

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