Abstract
Cyclo[18]carbon (C18) 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.
| Original language | English |
|---|---|
| Pages (from-to) | 6701-6705 |
| Number of pages | 5 |
| Journal | Journal of Physical Chemistry Letters |
| Volume | 10 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - 7 Nov 2019 |
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ASJC Scopus subject areas
- Materials Science(all)
- Physical and Theoretical Chemistry
Cite this
Cyclo[18]carbon : Insight into Electronic Structure, Aromaticity, and Surface Coupling. / Baryshnikov, Glib V.; Valiev, Rashid R.; Kuklin, Artem V.; Sundholm, Dage; Ågren, Hans.
In: Journal of Physical Chemistry Letters, Vol. 10, No. 21, 07.11.2019, p. 6701-6705.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Cyclo[18]carbon
T2 - Insight into Electronic Structure, Aromaticity, and Surface Coupling
AU - Baryshnikov, Glib V.
AU - Valiev, Rashid R.
AU - Kuklin, Artem V.
AU - Sundholm, Dage
AU - Ågren, Hans
PY - 2019/11/7
Y1 - 2019/11/7
N2 - Cyclo[18]carbon (C18) 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.
AB - Cyclo[18]carbon (C18) 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.
UR - http://www.scopus.com/inward/record.url?scp=85073878759&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85073878759&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.9b02815
DO - 10.1021/acs.jpclett.9b02815
M3 - Article
C2 - 31609631
AN - SCOPUS:85073878759
VL - 10
SP - 6701
EP - 6705
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
SN - 1948-7185
IS - 21
ER -