The average local ionization energy as a tool for identifying reactive sites on defect-containing model graphene systems

In a continuing effort to further explore the use of the average local ionization energy as a computational tool, we have investigated how well computed on molecular surfaces serves as a predictive tool for identifying the sites of the more reactive electrons in several nonplanar defect-containing m...

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Bibliographic Details
Published in:Journal of molecular modeling 2013-07, Vol.19 (7), p.2825-2833
Main Authors: Murray, Jane S., Shields, Zenaida Peralta-Inga, Lane, Pat, Macaveiu, Laura, Bulat, Felipe A.
Format: Article
Language:English
Subjects:
Catalytic Domain
Characterization and Evaluation of Materials
Chemistry
Chemistry and Materials Science
Computer Appl. in Life Sciences
Computer Applications in Chemistry
Computer Simulation
Electrons
Graphite - chemistry
Models, Molecular
Molecular Medicine
Original Paper
Surface Properties
Theoretical and Computational Chemistry
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Summary:In a continuing effort to further explore the use of the average local ionization energy as a computational tool, we have investigated how well computed on molecular surfaces serves as a predictive tool for identifying the sites of the more reactive electrons in several nonplanar defect-containing model graphene systems, each containing one or more pentagons. They include corannulene (C 20 H 10 ), two inverse Stone-Thrower-Wales defect-containing structures C 26 H 12 and C 42 H 16 , and a nanotube cap model C 22 H 6 , whose end is formed by three fused pentagons. Coronene (C 24 H 12 ) has been included as a reference planar defect-free graphene model. We have optimized the structures of these systems as well as several monohydrogenated derivatives at the B3PW91/6-31G* level, and have computed their on molecular surfaces corresponding to the 0.001 au, 0.003 au and 0.005 au contours of the electronic density. We find that (1) the convex sides of the interior carbons of the nonplanar models are more reactive than the concave sides, and (2) the magnitudes of the lowest surface minima (the ) correlate well with the interaction energies for hydrogenation at these sites. These values decrease in magnitude as the nonplanarity of the site increases, consistent with earlier studies. A practical benefit of the use of is that a single calculation suffices to characterize the numerous sites on a large molecular system, such as graphene and defect-containing graphene models. Figure Convex 0.001 au molecular surface of hydrogenated inverse Stone-Thrower-Wales defect-containing model 4H, with the hydrogen attached to one of the central carbons fusing the two pentagons
ISSN:1610-2940
0948-5023
DOI:10.1007/s00894-012-1693-8