We present a theoretical investigation of the hydrogenation of pyrene and of the subsequent molecular hydrogen evolution. Using density functional theory (DFT) at the GGA-PBE level, the chemical binding of atomic hydrogen to pyrene is found to be exothermic by up to 1.6 eV with a strong site dependence. The edge C atoms are found most reactive. The barrier for the formation of the hydrogen–pyrene bond is small, down to 0.06 eV. A second hydrogen binds barrierless at many sites. The most stable structure of dihydrogenpyrene is more stable by 0.64 eV than pyrene plus a molecular hydrogen molecule and a large barrier of 3.7 eV for the molecular hydrogen evolution is found. Using a simple tight-binding model we demonstrate that the projected density of π-states can be used to predict the most stable binding sites for hydrogen atoms and the model is used to investigate the most favorable binding sites on more hydrogenated pyrene molecules and on coronene. Some of the DFT calculations were complemented with hybrid-DFT (PBE0) showing a general agreement between the DFT and hybrid-DFT results.
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28 April 2011
Research Article|
April 29 2011
Pyrene: Hydrogenation, hydrogen evolution, and π-band model
Jakob Arendt Rasmussen;
Jakob Arendt Rasmussen
1Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Ny Munkegade, Building 1520,
Aarhus University
, DK-8000 Aarhus C, Denmark
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Graeme Henkelman;
Graeme Henkelman
2Department of Chemistry and Biochemistry,
The University of Texas at Austin
, Austin, Texas 78712-0165, USA
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Bjørk Hammer
Bjørk Hammer
a)
1Interdisciplinary Nanoscience Center (iNANO) and Department of Physics and Astronomy, Ny Munkegade, Building 1520,
Aarhus University
, DK-8000 Aarhus C, Denmark
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a)
Author to whom correspondence should be addressed. Electronic mail: [email protected].
J. Chem. Phys. 134, 164703 (2011)
Article history
Received:
November 12 2010
Accepted:
February 16 2011
Citation
Jakob Arendt Rasmussen, Graeme Henkelman, Bjørk Hammer; Pyrene: Hydrogenation, hydrogen evolution, and π-band model. J. Chem. Phys. 28 April 2011; 134 (16): 164703. https://doi.org/10.1063/1.3563632
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