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Rydberg electron stabilizes the charge localized state of the diamine cation

Author

Listed:
  • Marc Reimann

    (Technische Universität Berlin)

  • Christoph Kirsch

    (Martin-Luther-University Halle-Wittenberg)

  • Daniel Sebastiani

    (Martin-Luther-University Halle-Wittenberg)

  • Martin Kaupp

    (Technische Universität Berlin)

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.

Suggested Citation

  • Marc Reimann & Christoph Kirsch & Daniel Sebastiani & Martin Kaupp, 2024. "Rydberg electron stabilizes the charge localized state of the diamine cation," Nature Communications, Nature, vol. 15(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:15:y:2024:i:1:d:10.1038_s41467-023-44526-y
    DOI: 10.1038/s41467-023-44526-y
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    References listed on IDEAS

    as
    1. Zulfikhar A. Ali & Fredy W. Aquino & Bryan M. Wong, 2018. "The diamine cation is not a chemical example where density functional theory fails," Nature Communications, Nature, vol. 9(1), pages 1-3, December.
    2. Xinxin Cheng & Yao Zhang & Elvar Jónsson & Hannes Jónsson & Peter M. Weber, 2016. "Charge localization in a diamine cation provides a test of energy functionals and self-interaction correction," Nature Communications, Nature, vol. 7(1), pages 1-6, April.
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    Cited by:

    1. Hongni Chen & Chao Wang & Han Wu & Lili Li & Yali Xing & Chuanhui Zhang & Xiaojing Long, 2024. "Host-guest-induced electronic state triggers two-electron oxygen reduction electrocatalysis," Nature Communications, Nature, vol. 15(1), pages 1-14, December.

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