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

[en] 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. © 2017 the Owner Societies.

Disciplines :

Chemistry

Author, co-author :

Bohl, E. ^✱; EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, United Kingdom

Mignolet, Benoît ^✱; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique

Johansson, J. O.; EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, United Kingdom

Remacle, Françoise ; Université de Liège - ULiège > Département de chimie (sciences) > Laboratoire de chimie physique théorique

Campbell, E. E. B.; EaStCHEM, School of Chemistry, University of Edinburgh, Edinburgh, United Kingdom, Division of Quantum Phases and Devices, School of Physics, Konkuk University, Seoul 05029, South Korea

^✱ These authors have contributed equally to this work.

Language :

English

Title :

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

Publication date :

2017

Journal title :

Physical Chemistry Chemical Physics

ISSN :

1463-9076

eISSN :

1463-9084

Publisher :

Royal Society of Chemistry

Volume :

Issue :

Pages :

24090-24099

Peer reviewed :

Peer Reviewed verified by ORBi

Tags :

CÉCI : Consortium des Équipements de Calcul Intensif

Funders :

F.R.S.-FNRS - Fonds de la Recherche Scientifique

Funding text :

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.

Available on ORBi :

since 17 December 2017

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