Cyclo[18]carbon: Insight into Electronic Structure, Aromaticity, and Surface Coupling

Glib V. Baryshnikov, Rashid R. Valiev, Artem V. Kuklin, Dage Sundholm, Hans Ågren

Research output: Contribution to journalArticle

3 Citations (Scopus)

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 languageEnglish
Pages (from-to)6701-6705
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume10
Issue number21
DOIs
Publication statusPublished - 7 Nov 2019

Fingerprint

Electronic structure
Carbon
electronic structure
functionals
Density functional theory
carbon
density functional theory
Adsorption
adsorption
Geometry
Electron transitions
geometry
Ground state
Molecular structure
molecular structure
ground state
energy

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 journalArticle

Baryshnikov, Glib V. ; Valiev, Rashid R. ; Kuklin, Artem V. ; Sundholm, Dage ; Ågren, Hans. / Cyclo[18]carbon : Insight into Electronic Structure, Aromaticity, and Surface Coupling. In: Journal of Physical Chemistry Letters. 2019 ; Vol. 10, No. 21. pp. 6701-6705.
@article{5d62d110e0754840b61ef4629153568c,
title = "Cyclo[18]carbon: Insight into Electronic Structure, Aromaticity, and Surface Coupling",
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 H{\"u}ckel 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.",
author = "Baryshnikov, {Glib V.} and Valiev, {Rashid R.} and Kuklin, {Artem V.} and Dage Sundholm and Hans {\AA}gren",
year = "2019",
month = "11",
day = "7",
doi = "10.1021/acs.jpclett.9b02815",
language = "English",
volume = "10",
pages = "6701--6705",
journal = "Journal of Physical Chemistry Letters",
issn = "1948-7185",
publisher = "American Chemical Society",
number = "21",

}

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 -