Superhydrogenation of pentacene: the reactivity of zigzag-edges

Campisi, Dario; Simonsen, Frederik Doktor S.; Thrower, J. D.; Jaganathan, Rijutha; Hornekær, Liv; Martinazzo, Rocco; Tielens, A. G. G. M.

doi:10.1039/c9cp05440e

Cited by 24 publications

(35 citation statements)

References 54 publications

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“…Quantum chemical methods can play an important role in identifying chemical routes and reaction products. 5 , 6 , 86 , 87 However, due to the large computational cost, little has been done to study the chemical and physical properties of PAHs on minerals. 53 , 54 In this work, we identified a DFT method that can accurately compute the binding energy of aromatic molecules on a mineral surface.…”

Section: Discussionmentioning

confidence: 99%

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

et al. 2021

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Density functional theory (DFT) has provided deep atomic-level insights into the adsorption behavior of aromatic molecules on solid surfaces. However, modeling the surface phenomena of large molecules on mineral surfaces with accurate plane wave methods (PW) can be orders of magnitude more computationally expensive than localized atomic orbitals (LCAO) methods. In the present work, we propose a less costly approach based on the DFT-D4 method (PBE-D4), using LCAO, to study the interactions of aromatic molecules with the {010} forsterite (Mg 2 SiO 4 ) surface for their relevance in astrochemistry. We studied the interaction of benzene with the pristine {010} forsterite surface and with transition-metal cations (Fe 2+ and Ni 2+ ) using PBE-D4 and a vdW-inclusive density functional (Dion, Rydberg, Schröder, Langreth, and Lundqvist (DRSLL)) with LCAO methods. PBE-D4 shows good agreement with coupled-cluster methods (CCSD(T)) for the binding energy trend of cation complexes and with PW methods for the binding energy of benzene on the forsterite surface with a difference of about 0.03 eV. The basis set superposition error (BSSE) correction is shown to be essential to ensure a correct estimation of the binding energies even when large basis sets are employed for single-point calculations of the optimized structures with smaller basis sets. We also studied the interaction of naphthalene and benzocoronene on pristine and transition-metal-doped {010} forsterite surfaces as a test case for PBE-D4. Yielding results that are in good agreement with the plane wave methods with a difference of about 0.02–0.17 eV, the PBE-D4 method is demonstrated to be effective in unraveling the binding structures and the energetic trends of aromatic molecules on pristine and transition-metal-doped forsterite mineral surfaces. Furthermore, PBE-D4 results are in good agreement with its predecessor PBE-D3(BJM) and with the vdW-inclusive density functionals, as long as transition metals are not involved. Hence, PBE-D4/CP-DZP has been proven to be a robust theory level to study the interaction of aromatic molecules on mineral surfaces.

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Section: Discussionmentioning

confidence: 99%

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

et al. 2021

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“…These are the sites where we expect that the second hydrogen will most likely chemisorb as seen for coronene and pentacene molecules. 26,42 The other isomers analysed have the population of spin-up electrons distributed more uniformly over the entire carbon framework.…”

Section: Hydrogenation Processmentioning

confidence: 99%

Do defects in PAHs promote catalytic activity in space? Stone–Wales pyrene as a test case

Campisi

Candian

2020

Phys. Chem. Chem. Phys.

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“…In other words, it proves that our EA based search method is capable of predicting low energy dimers in an unbiased and precise fashion. Meanwhile, the structure of the global minimum, dimer-I indicates the special hydrogen affinity of central edge carbon atoms in pentacene 36 .…”

Section: B Pentacenementioning

confidence: 99%

Dimerization of dehydrogenated polycyclic aromatic hydrocarbons on graphene

Tang

Hammer

2022

The Journal of Chemical Physics

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Dimerization of polycyclic aromatic hydrocarbons (PAHs) is an important, yet poorly understood, step in the on-surface synthesis of graphene (nanoribbon), soot formation, and growth of carbonaceous dust grains in the interstellar medium (ISM). The on-surface synthesis of graphene and the growth of carbonaceous dust grains in the ISM require the chemical dimerization in which chemical bonds are formed between PAH monomers. An accurate and cheap method of exploring structure rearrangements is needed to reveal the mechanism of chemical dimerization on surfaces. This work has investigated the chemical dimerization of two dehydrogenated PAHs (coronene and pentacene) on graphene via an evolutionary algorithm augmented by machine learning surrogate potentials and a set of customized structure operators. Different dimer structures on surfaces have been successfully located by our structure search methods. Their binding energies are within the experimental errors of temperature programmed desorption measurements. The mechanism of coronene dimer formation on graphene is further studied and discussed.

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Superhydrogenation of pentacene: the reactivity of zigzag-edges

Abstract: Studies of pentacene hydrogenation reveal a preferential hydrogenation sequence. The guiding concepts apply more broadly to aromatic carbonaceous systems and may be crucial in catalytic formation of molecular hydrogen in interstellar space.

Cited by 24 publications

References 54 publications

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

Interaction of Aromatic Molecules with Forsterite: Accuracy of the Periodic DFT-D4 Method

Do defects in PAHs promote catalytic activity in space? Stone–Wales pyrene as a test case

Dimerization of dehydrogenated polycyclic aromatic hydrocarbons on graphene

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