Low-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes

E. Bohl; B. Mignolet; J. O. Johansson; F. Remacle; E. E.B. Campbell

doi:10.1039/c7cp03913a

Low-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes

E. Bohl, B. Mignolet, J. O. Johansson, F. Remacle, E. E.B. Campbell

Department of Physics

Research output: Contribution to journal › Article › peer-review

13 Scopus citations

Abstract

TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.

Original language	English
Pages (from-to)	24090-24099
Number of pages	10
Journal	Physical Chemistry Chemical Physics
Volume	19
Issue number	35
DOIs	https://doi.org/10.1039/c7cp03913a
State	Published - 2017

Bibliographical note

Funding Information:
The authors thank A. V. Bulgakov for helpful discussions. E. B., J. O. J. and E. E. B. C. gratefully acknowledge financial support from the Leverhulme Foundation (RPF-298 ‘‘PES of hollow nanomaterials’’). JOJ is a Royal Society of Edinburgh/BP Trust Research Fellow. BM and FR acknowledge support from the Fonds National de la Recherche Scientifique (FNRS), Belgium and from the Consortium des Equipements de Calcul Intensif (CECI) for computational resources (FNRS 2.5020.11) and of the FNRS research project T.0132.16.

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© 2017 the Owner Societies.

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title = "Low-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes",

abstract = "TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small {"}hollow{"} carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.",

author = "E. Bohl and B. Mignolet and Johansson, {J. O.} and F. Remacle and Campbell, {E. E.B.}",

note = "Funding Information: The authors thank A. V. Bulgakov for helpful discussions. E. B., J. O. J. and E. E. B. C. gratefully acknowledge financial support from the Leverhulme Foundation (RPF-298 {\textquoteleft}{\textquoteleft}PES of hollow nanomaterials{\textquoteright}{\textquoteright}). JOJ is a Royal Society of Edinburgh/BP Trust Research Fellow. BM and FR acknowledge support from the Fonds National de la Recherche Scientifique (FNRS), Belgium and from the Consortium des Equipements de Calcul Intensif (CECI) for computational resources (FNRS 2.5020.11) and of the FNRS research project T.0132.16. Publisher Copyright: {\textcopyright} 2017 the Owner Societies.",

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language = "English",

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AU - Bohl, E.

AU - Mignolet, B.

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AU - Remacle, F.

AU - Campbell, E. E.B.

N1 - Funding Information: The authors thank A. V. Bulgakov for helpful discussions. E. B., J. O. J. and E. E. B. C. gratefully acknowledge financial support from the Leverhulme Foundation (RPF-298 ‘‘PES of hollow nanomaterials’’). JOJ is a Royal Society of Edinburgh/BP Trust Research Fellow. BM and FR acknowledge support from the Fonds National de la Recherche Scientifique (FNRS), Belgium and from the Consortium des Equipements de Calcul Intensif (CECI) for computational resources (FNRS 2.5020.11) and of the FNRS research project T.0132.16. Publisher Copyright: © 2017 the Owner Societies.

PY - 2017

Y1 - 2017

N2 - TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.

AB - TD-DFT calculations of low-lying, Rydberg states of a series of polycyclic hydrocarbons and cyclic alkanes are presented. Systematic variations in binding energies and photoelectron angular distributions for the first members of the s, p and d Rydberg series are predicted for increasing molecular complexity. Calculated binding energies are found to be in very good agreement with literature values where they exist for comparison. Experimental angle-resolved photoelectron spectroscopy results are presented for coronene, again showing very good agreement with theoretical predictions of binding energies and also for photoelectron angular distributions. The Dyson orbitals for the small "hollow" carbon structures, cubane, adamantane and dodecahedrane, are shown to have close similarities to atomic s, p and d orbitals, similar to the superatom molecular orbitals (SAMOs) reported for fullerenes, indicating that these low-lying, diffuse states are not restricted to π-conjugated molecules.

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JO - Physical Chemistry Chemical Physics

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ER -

Low-lying, Rydberg states of polycyclic aromatic hydrocarbons (PAHs) and cyclic alkanes

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