Cyclo[18]carbon: Insight into Electronic Structure, Aromaticity, and Surface Coupling
Open accessAbstract
Cyclo[18]carbon (C 18 ) is studied computationally at the density functional theory (DFT) and ab initio levels to obtain insight into its electronic structure, aromaticity, and adsorption properties on a NaCl surface. DFT functionals with a small amount of Hartree–Fock exchange fail to determine the experimentally observed polyyne molecular structure, revealing a cumulene-type geometry. Exchange-correlation functionals with a large amount of Hartree–Fock exchange as well as ab initio CASSCF calculations yield the polyyne structure as the ground state and the cumulene structure as a transition state between the two inverted polyyne structures through a Kekule distortion. The polyyne and the cumulene structures are found to be doubly Hückel aromatic. The calculated adsorption energy of cyclo[18]carbon on the NaCl surface is small (37 meV/C) and almost the same for both structures, implying that the surface does not stabilize a particular geometry.
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For C4n+2 (n = 3-6) molecules, QST2 and IRC calculations generated cumulenic geometries with equal bond lengths and alternating bond angles, adopting D(n/2)h point-group symmetry, as transition states between two inversion-related polyynic ground states.
“For C 4n+2 (n = 3-6) molecules, QST2 and IRC calculations generated cumulenic geometries with equal bond lengths and altering bond angles, adopting D (n/2)h point group symmetry, as transition states between two inversion related polyynic ground states 28 (Fig. 2).”
From Induced magnetic field in sp-hybridized carbon rings: analysis of double aromaticity and antiaromaticity in cyclo[2 <i>N</i> ]carbon allotropes (2020) · cites this paper as [28]
Split into 2 atoms — 0 confirmed, 2 partially supported, 0 disputed, 0 misattributed, 0 unverifiable. Expand the claim to see per-atom verdicts.
Experimental — accuracy not yet measuredp_out orbitals induce stronger diatropic currents than p_in, both in polyynic and cumulenic geometries of C18.
“Moreover, although the GIMIC method does not yet allow the dissection of ring current to contributions from different sets of orbitals, it obtained the current strengths of p out and p in sets by integrating the current density within distinctive contours and found that p out orbitals induce stronger diatropic currents than p in , both in polyynic and cumulenic geometries.”
From Induced magnetic field in sp-hybridized carbon rings: analysis of double aromaticity and antiaromaticity in cyclo[2 <i>N</i> ]carbon allotropes (2020) · cites this paper as [28]
In the paper’s GIMIC discussion (page unavailable), reduced-contour calculations give Iout = 21.8 and Iin = 7.2 nA T⁻¹ for the polyyne geometry, supporting the stronger out-of-plane current there. The same passage reports a larger total diatropic current for the cumulene transition-state geometry, but does not compare its out-of-plane and in-plane contributions. (LLM, conf=0.86)
Experimental — accuracy not yet measuredThe cumulenic structure of C18 has been predicted to be a transition state between two degenerate polyynic ground states with inverted single-triple bonds.
“Moreover, the cumulenic structure has been predicted to be a transition state between two degenerate polyynic ground states with inverted single-triple bonds.25,28,30”
From Induced magnetic field in sp-hybridized carbon rings: analysis of double aromaticity and antiaromaticity in cyclo[2 <i>N</i> ]carbon allotropes (2020) · cites this paper as [28]
Baryshnikov et al. reported that the polyynic structure of C18 induces a strong diatropic current which is much weaker than the diatropic current of cumulene.
“Recently Baryshnikov et al. 28 employed the GIMIC method to measure the ring currents of both polyynic and cumulenic configurations of C 18 and reported that the polyynic structure induces a strong diatropic current which is however much weaker than the diatropic current of cumulene.”
From Induced magnetic field in sp-hybridized carbon rings: analysis of double aromaticity and antiaromaticity in cyclo[2 <i>N</i> ]carbon allotropes (2020) · cites this paper as [28]
C18 was described as doubly aromatic based on 4n+2 number of π electrons and development of diatropic ring currents under a perpendicular magnetic field.
“This compound was described as doubly aromatic based on 4n + 2 number of π electrons and development of diatropic ring currents under the influence of a perpendicular magnetic field [118-121].”
From Aromaticity and Antiaromaticity: How to Define Them (2025) · cites this paper as [121]
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“GIMIC and ACID analyses demonstrated that the ring currents in these molecules originate from both in-plane and out- of-plane π-electrons, supporting the concept of double aromaticity in these systems [11, 13, 17, 29].”
- Authors
- Baryshnikov, G. V., Valiev, R. R., Kuklin, A. V., Sundholm, D., & Ågren, H.
- Affiliations
- Cherkasy National University (UA)
- University of Helsinki (FI)
- Siberian Federal University (RU)
- Henan University (CN)
- Corresponding author
- Baryshnikov, Glib V.
- Ågren, Hans
- Venue
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Published
- 2019-10-14
- Volume
- 10
- Issue
- 21
- Pages
- 6701-6705
- ISSN
- 1948-7185 (ISSN-L)
- OpenAlex
- W2981075862
- Cited by
- 170
- References
- 36
- Citations by year
- 2026: 12 · 2025: 27 · 2024: 26 · 2023: 27 · 2022: 26 · 2021: 21 · 2020: 25 · 2019: 6
- FWCI
- 8.57
- Type
- journal article
- Language
- en
- Open access
- green
- hdl.handle.net
- Licence
- Locations
- The Journal of Physical Chemistry Letters (publishedVersion)
- PubMed (publishedVersion)
- Työväentutkimus Vuosikirja (submittedVersion, other-oa)
- SibFU Digital Repository (Siberian Federal University) (submittedVersion)
- Funders
- Russian Science Foundation (19-73-10015)
- Stiftelsen Olle Engkvist Byggm?stare (189-0223)
- Academy of Finland (1325369)
- Ministry of Education and Science of Ukraine (0117U003908)
- Tomsk Polytechnic University Competitiveness Enhancement Program (VIU-RSCABS-142/2019)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
- Physical Sciences › Chemistry › Organic Chemistry › Synthesis and Properties of Aromatic Compounds
- Physical Sciences › Chemistry › Organic Chemistry › Fullerene Chemistry and Applications
- Keywords
- cyclo[18]carbon, polyynes, cumulenes, aromaticity, Hückel aromaticity, Kekulé distortion, exchange-correlation functionals, CASSCF, NaCl surface, adsorption energy, surface coupling, ground state structure, transition state
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