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

Campisi, Dario; Candian, Alessandra

doi:10.1039/c9cp06523g

Cited by 10 publications

(12 citation statements)

References 60 publications

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“…The first hydrogen atom to bond with the graphene sheet must overcome a calculated activation barrier of around 0.16 eV to chemisorb, , close to the experimentally determined value of 0.2 eV . This barrier can be overcome by rapid, quasi-elastic energy loss by the impinging hydrogen atom. , The Stone–Wales defect was found to lower the barrier toward the initial C–H bond formation in a pyrene model system . No activation barrier is found for a second hydrogen atom forming a C–H dimer at the para carbon positions, ,− though bonding competes with H 2 recombination and abstraction at the ortho position.…”

Section: Introductionsupporting

confidence: 63%

“…27,28 The Stone−Wales defect was found to lower the barrier toward the initial C−H bond formation in a pyrene model system. 29 activation barrier is found for a second hydrogen atom forming a C−H dimer at the para carbon positions, 27,30−32 though bonding competes with H 2 recombination and abstraction at the ortho position. It is possible that instead of chemisorbing, a second hydrogen atom could physisorb and remain mobile on the surface.…”

Section: Introductionmentioning

confidence: 99%

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Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model

2021

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A preexisting chemisorbed defect is well-known to increase the reactivity of graphene which is normally chemically inert. Specifically, the presence of chemisorbed hydrogen atoms forming an sp3-hybridized C–H bond is known to increase the reactivity of neighboring carbon atoms toward additional hydrogenation with wide-ranging applications from materials science to astrochemistry. In this work, static DFT and DFT-based direct dynamics simulations are used to characterize the reactivity of a graphene sheet around an existing C–H bond defect. The spin density landscape shows how to guide subsequent H atom additions, always bonding most strongly to the carbon atom with greatest spin density. Molecular dynamics of an impinging H atom under thermal conditions with defect graphene was used to determine the statistics of probable reactions. The most frequent outcome is inelastic scattering (48%) and then Eley–Rideal (ER) abstraction of the chemisorbed H atom as vibrationally hot H2 (40%), while the least likely, but probably most interesting, result is formation of a novel C–H bond (12%). The C–H bonds always form in the β sublattice. The carbon atom in the para position shows to be most reactive toward the incoming H atom, followed by the ortho carbon, in agreement with the spin density computed in the static calculations. Globally, the graphene energy surface is repulsive, but the defects create local channels into this energy surface through which reactants can move locally through and react with the activated surface without a barrier.

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Section: Introductionsupporting

confidence: 63%

Section: Introductionmentioning

confidence: 99%

Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model

2021

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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%

“…They have been identified through their vibrational signature in infrared spectra and thought to be involved in many important processes that regulate the physical conditions of star-forming regions . Specifically, PAHs have been extensively studied as catalysts for interstellar H 2 formation. − They may also play a role as reagents in many reactions involving atoms, ions, and molecules that contribute to the rich organic inventory of space . Finally, it has been suggested that PAHs may be more directly involved in the origin of life by providing a convenient assemblage structure for RNA …”

Section: Introductionmentioning

confidence: 99%

“…However, studies on astronomically relevant mineral surfaces are sorely lacking . Specifically, while quantum chemistry and in particular density functional theory (DFT) are well established as important tools in assessing the relevance of gas-phase reactions of PAHs to space, − , studies on the interaction of molecular species with mineral species have lagged due to the prohibitive computational costs and the challenges in employing hybrid functionals that correct the self-interaction error of standard (semilocal) DFT methods . In material sciences, plane wave (PW) codes such as VASP have been widely employed as they ensure robust and accurate results. − However, plane wave codes allow modeling of molecules of limited size due to their computational cost .…”

Section: Introductionmentioning

confidence: 99%

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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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The road to bis‐periazulene (cyclohepta[def]fluorene): Realizing one of the long‐standing dreams in nonalternant hydrocarbons

Konishi

Horii

Yasuda

2023

J of Physical Organic Chem

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

Abstract: Using density functional theory (DFT), we studied the formation of H2 on Stone–Wales pyrene.

Cited by 10 publications

References 60 publications

Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model

Exploration of Graphene Defect Reactivity toward a Hydrogen Radical Utilizing a Preactivated Circumcoronene Model

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

The road to bis‐periazulene (cyclohepta[def]fluorene): Realizing one of the long‐standing dreams in nonalternant hydrocarbons

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