Vibrational stabilization in cyclacene carbon nanobelts
Vibrational stabilization in cyclacene carbon nanobelts
Cyclacene carbon nanobelts are predicted to be more stable in certain vibrational states. Vibrational simulations using hybrid thermally assisted-occupation density functional theory (TAO−DFT) predict small but consistent singlet−triplet electronic excitation energy changes at the classical harmonic vibrational turning points of the smaller belts. Geometric and vibrational properties are also compared between hybrid Kohn−Sham DFT and TAO−DFT for [n]cyclacene (n = 6−14), where TAO−DFT is found to shorten the carbon−carbon bonds bridging between the two annulene ribbons and causes qualitative changes in the calculated infrared spectra. These geometric changes lower the singlet−triplet transition energies and introduce greater ring strain, while individual vibrational modes are observed to shift by over 200 cm−1. These findings indicate that including static correlation is important for describing both the geometric and vibrational properties of cyclacenes accurately.
8601-8612
Hanson-Heine, Magnus W.D.
6510092a-643b-4f74-91f7-55bf236636a6
4 September 2025
Hanson-Heine, Magnus W.D.
6510092a-643b-4f74-91f7-55bf236636a6
Hanson-Heine, Magnus W.D.
(2025)
Vibrational stabilization in cyclacene carbon nanobelts.
Journal of Physical Chemistry A, 129 (37), .
(doi:10.1021/acs.jpca.5c04863).
Abstract
Cyclacene carbon nanobelts are predicted to be more stable in certain vibrational states. Vibrational simulations using hybrid thermally assisted-occupation density functional theory (TAO−DFT) predict small but consistent singlet−triplet electronic excitation energy changes at the classical harmonic vibrational turning points of the smaller belts. Geometric and vibrational properties are also compared between hybrid Kohn−Sham DFT and TAO−DFT for [n]cyclacene (n = 6−14), where TAO−DFT is found to shorten the carbon−carbon bonds bridging between the two annulene ribbons and causes qualitative changes in the calculated infrared spectra. These geometric changes lower the singlet−triplet transition energies and introduce greater ring strain, while individual vibrational modes are observed to shift by over 200 cm−1. These findings indicate that including static correlation is important for describing both the geometric and vibrational properties of cyclacenes accurately.
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Vibrational Stabilization in Cyclacene Carbon Nanobelts
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Accepted/In Press date: 26 August 2025
Published date: 4 September 2025
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For the purpose of open access, the author has applied a Creative Commons attribution license (CC BY) to any Author Accepted Manuscript version arising from this submission.
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Local EPrints ID: 506161
URI: http://eprints.soton.ac.uk/id/eprint/506161
ISSN: 1089-5639
PURE UUID: 7e00de23-875b-4b18-98e5-8cd75f458bcf
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Date deposited: 29 Oct 2025 17:40
Last modified: 30 Oct 2025 03:14
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Author:
Magnus W.D. Hanson-Heine
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