Computational study of the addition of molecular oxygen to benzene

Cheikh, F.; Boucekkine, Abdou; Cartier, Alain

doi:10.1016/s0166-1280(96)04878-6

Cited by 9 publications

(17 citation statements)

References 16 publications

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“…For example, the O 2 -benzene ͑neutral-neutral͒ dissociation energy is known to be about 0.05 eV. [29][30][31] This value can be neglected in comparison with the magnitudes of the spectral shifts ͑E.A. differences͒ encountered here.…”

Section: B Anion-neutral Interaction Energy Determinationsmentioning

confidence: 84%

Microsolvation of small anions by aromatic molecules: An exploratory study

Barbu

Schiedt

Weinkauf

et al. 2002

The Journal of Chemical Physics

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This work was motivated by the experimental finding that the O 2 Ϫ /benzene interaction energy is unexpectedly large. To further explore the interactions of small anions with aromatic molecules, anion photoelectron spectroscopy was utilized to measure interaction strengths of the seed anions, O 2 Ϫ and NO Ϫ , complexed with several aromatic molecules, including benzene, naphthalene, pyridine, and pyrimidine. As in the case of O 2 Ϫ ͑benzene͒, the anion͑aromatic͒ 1 binding energies for the other complexes studied were also higher than one might have anticipated. In addition, the interaction energy of O 2 Ϫ complexed with a given aromatic molecule was, in every case studied, higher ͑by a factor of ϳ1.5͒ than that of NO Ϫ complexed with the same aromatic. While the dependence of interaction strengths on solvent dipole moments and/or polarizabilities implied a substantial electrostatic component to the binding in these complexes, differences in the binding of O 2 Ϫ and NO Ϫ with these aromatic molecules showed that there is a distinct covalent aspect to the interaction as well. A significant portion of this interaction was attributed to the fact that O 2 Ϫ and NO Ϫ are both open-shell anions that are interacting with closed-shell aromatic molecules. In the accompanying paper ͓J. Chem. Phys. 116, 9672 ͑2002͔͒ calculations on O 2 Ϫ ͑benzene͒ 1 by Jalbout and Adamowicz shed additional light on the nature of small anion-aromatic molecule interactions. Last, results are also presented comparing the interaction energies of several multisolvent, anionmolecule complexes.

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Section: B Anion-neutral Interaction Energy Determinationsmentioning

confidence: 84%

Microsolvation of small anions by aromatic molecules: An exploratory study

Barbu

Schiedt

Weinkauf

et al. 2002

The Journal of Chemical Physics

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“…Likewise, linear hydrocarbons (HCs) such as ethene (C 2 H 4 ) and propane (C 3 H 8 ), [207–209] and alkyl benzenes display notable improvements in combustion parameters with the addition of singlet O 2. [15,210,211] The latter group constitutes a significant additive fraction in transportation fuels, e. g., gasoline and diesel [212,213] . To date, many experimental results and computational simulations proved the considerable impact of singlet oxygen on accelerating the chain‐branching mechanism, decreasing the ignition temperature as well as the induction time [188,190–196] .…”

Section: Implications Of Singlet Oxygen In Combustion and Advanced Oxmentioning

confidence: 99%

Review of Chemical Reactivity of Singlet Oxygen with Organic Fuels and Contaminants

Al-Nu’airat

Oluwoye

Zeinali

et al. 2020

The Chemical Record

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Singlet oxygen represents a form of reactive oxygen species (ROS), produced by electronic excitation of molecular triplet oxygen. In general, highly reactive oxygen‐bearing molecules remain the backbone of diverse ground‐breaking technologies, driving the waves of scientific development in environmental, biotechnology, materials, medical and defence sciences. Singlet oxygen has a relatively high energy of about 94 kJ/mol compared to the ground state molecular O2 and therefore initiates low‐temperature oxidation of electron‐rich hydrocarbons. Such reactivity of singlet oxygen has inspired a wide array of emerging applications in chemical, biochemical and combustion phenomena. This paper reviews the intrinsic properties of singlet oxygen, emphasising the physical aspects of its natural occurrences, production techniques, as well as chemical reactivity with organic fuels and contaminants. The review assembles critical scientific studies on the implications of singlet oxygen in initiating chemical reactions, identifying, and quantitating the consequential effects on combustion, fire safety, as well as on the low‐temperature treatment of organic wastes and contaminants. Moreover, the content of this review appraises computational efforts, such as DFT quantum mechanical modelling, in developing mechanistic (i. e., both thermodynamic and kinetic) insights into the reaction of singlet oxygen with hydrocarbons.

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“…The reaction mechanism of singlet oxygen ( 1 Δ g ‐O 2 ) with benzene has been extensively studied theoretically . A frontier molecular orbital investigation of the reaction of acenes with 1 Δ g ‐O 2 was published 30 years ago .…”

Section: Reactivity Of Acenes Toward Oxygenmentioning

confidence: 99%

Reactivity of acenes: mechanisms and dependence on acene length

Zade

Bendikov

2012

J of Physical Organic Chem

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Acenes are polycyclic aromatic hydrocarbons consisting of linearly fused benzene rings. These compounds are currently the subject of great interest from both fundamental and applied perspectives, particularly for use in organic electronics. This review highlights the computational studies carried out to understand acene reactivity, their reaction mechanisms, and the relationship of the latter to acene length. Generally, as acene length increases, the reactivity of acenes increases, and a greater tendency towards a biradical mechanism is observed. For example, an interesting change in mechanism (from concerted to biradical) is observed for the reaction of acenes (benzene through pentacene) with molecular oxygen. A computational study of the addition of HCl (which behaves as an electrophile) and water (which behaves mostly as a nucleophile) to acenes revealed that acene reactivity increases along the series up to hexacene and remains constant from hexacene and above because of the biradical character of the ground state of higher acenes. Although the exothermicity of the addition of water and HCl to acene is similar, the activation barrier for the addition of water is significantly higher than that for HCl. There is a substantial substituent effect on the energy barriers for electrophilic and nucleophilic reactions. Phenyl substitution at the most reactive meso‐carbon atoms of the central ring of acene blocks dimerization through this ring but does not efficiently prevent dimerization through other rings. With respect to the self‐reactivity (such as dimerization, etc.) of acenes, a computational study showed that the preferred pathways are the formation of acene dimers via a central benzene ring and the formation of acene‐based polymers. Interestingly, longer acenes are predicted to self‐react to form polymers, rather than acene dimers, as the thermodynamically preferred product. These findings invite experimentalists to reinvestigate the dimerization of long unsubstituted acenes. Given that computational studies directly relate to the gas phase reactivity of acenes, whereas long acenes find application in organic semiconductor devices as solids, the next research challenge is to obtain an understanding of the solid state reactivity of long acenes. Copyright © 2012 John Wiley & Sons, Ltd.

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Computational study of the addition of molecular oxygen to benzene

Cited by 9 publications

References 16 publications

Microsolvation of small anions by aromatic molecules: An exploratory study

Microsolvation of small anions by aromatic molecules: An exploratory study

Review of Chemical Reactivity of Singlet Oxygen with Organic Fuels and Contaminants

Reactivity of acenes: mechanisms and dependence on acene length

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