Issue 2, 2017

Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

Abstract

We apply a combination of state-of-the-art experimental and quantum-chemical methods to elucidate the electronic and chemical energetics of hydrogen adduction to a model open-shell graphene fragment. The lowest-energy adduct, 1H-phenalene, is determined to have a bond dissociation energy of 258.1 kJ mol−1, while other isomers exhibit reduced or in some cases negative bond dissociation energies, the metastable species being bound by the emergence of a conical intersection along the high-symmetry dissociation coordinate. The gas-phase excitation spectrum of 1H-phenalene and its radical cation are recorded using laser spectroscopy coupled to mass-spectrometry. Several electronically excited states of both species are observed, allowing the determination of the excited-state bond dissociation energy. The ionization energy of 1H-phenalene is determined to be 7.449(17) eV, consistent with high-level W1X-2 calculations.

Graphical abstract: Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

Article information

Article type
Edge Article
Submitted
24 Aug 2016
Accepted
24 Sep 2016
First published
26 Sep 2016
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2017,8, 1186-1194

Hydrogen-adduction to open-shell graphene fragments: spectroscopy, thermochemistry and astrochemistry

G. D. O'Connor, B. Chan, J. A. Sanelli, K. M. Cergol, V. Dryza, R. J. Payne, E. J. Bieske, L. Radom and T. W. Schmidt, Chem. Sci., 2017, 8, 1186 DOI: 10.1039/C6SC03787A

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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