Quantum Chemistry Investigation of Key Reactions Involved in the Formation of Naphthalene and Indene

Fascella, Simone; Cavallotti, Carlo; Rota, Renato; Carrà, Sergio

doi:10.1021/jp037518k

Cited by 54 publications

(69 citation statements)

References 32 publications

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“…When necessary (i.e., for relatively small rotational energetic barriers), the corresponding partition function was calculated using a hindered rotor model, with energy levels determined solving the Schrodinger equation for a one-dimensional torsional rotation on a rotational potential surface computed at the B3LYP/6-31+G(d,p) level. 38 The moments of inertia for the torsional rotations were calculated with respect to the rotating bond axis and reduced to account for the conjunct rotation of the two moieties as I = I 1 I 2 /(I 1 + I 2 ). This approach corresponds to the I(2,1) level in the East and Radom classification.…”

Section: Computational Methodologymentioning

confidence: 99%

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis

et al. 2012

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The cyclopentadienyl radical (cC(5)H(5)) is among the most stable radical species that can be generated during the combustion and pyrolysis of hydrocarbons and it is generally agreed that its contribution to the gas phase reactivity is significant. In this study the kinetics of one key cC(5)H(5) reaction channel, namely the reaction between cC(5)H(5) and cyclopentadiene (cC(5)H(6)), was investigated using ab initio calculations and RRKM/Master Equation theory. It was found that most of the excited C(5)H(5)_C(5)H(6) adducts formed by the addition of cC(5)H(5) to cC(5)H(6) decompose back to reactants and that the major reaction products are, in order of importance, indene, vinylfulvene (a most probable styrene precursor), phenylbutadiene, and benzene. The preferred reaction pathway of the C(5)H(5)_C(5)H(6) adduct is started by the migration of the tertiary hydrogen of the C(5)H(5) ring to a vicinal carbon and followed by the β-opening of the C(5)H(6) ring, which is the rate determining step. Successive molecular rearrangements lead to decomposition to the four possible products. The kinetic constants for the four reaction channels, calculated at atmospheric pressure and interpolated in cm(3) mol(-1) s(-1) between 900 and 2000 K, are k(indene) = 10(25.197)T(-3.935) exp(-11630/T(K)), k(vinylfulvene) = 10(65.077)T(-14.20) exp(-37567/T(K)), k(benzene) = 10(29.172)T(-4.515) exp(-20570/T(K)), and k(phenylbutadiene) = 10(16.743)T(-1.407) exp(-11804/T(K)). The predictive capability of the reaction set so determined was tested through the simulations of recent cC(5)H(6) pyrolysis and combustion experiments using a detailed kinetic mechanism. A quantitative agreement with experimental data was obtained by assuming that vinylfulvene converts rapidly to stryrene, increasing its reaction channel by a factor of 2, and assuming that phenylbutadiene rapidly decomposes with equal probability to styrene and benzene.

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Section: Computational Methodologymentioning

confidence: 99%

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis

et al. 2012

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“…where V is the volume, m the particle mass, v i the vibrational frequency, I x I y I z the product of the three rotational constants, and σ the rotational symmetry number [67][68][69].…”

Section: Quantum Chemistrymentioning

confidence: 99%

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

2015

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Throughout the last 25 years, computational chemistry based on quantum mechanics has been applied to the investigation of reaction kinetics in free radical polymerization (FRP) with growing interest. Nowadays, quantum chemistry (QC) can be considered a powerful and cost-effective tool for the kinetic characterization of many individual reactions in FRP, especially those that cannot yet be fully analyzed through experiments. The recent focus on copolymers and systems where secondary reactions play a major role has emphasized this feature due to the increased complexity of these kinetic schemes. QC calculations are well-suited to support and guide the experimental investigation of FRP kinetics as well as to deepen the understanding of polymerization mechanisms. This paper is intended to provide an overview of the most relevant QC results obtained so far from the investigation of FRP. A comparison between computational results and experimental data is given, whenever possible, to emphasize the performances of the two approaches in the prediction of kinetic data. This work provides a comprehensive database of reaction rate parameters of FRP to assist in the development of advanced models of polymerization and experimental studies on the topic.

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“…(12) Fascella et al [29] ont proposé un mécanisme de formation des premiers HAP impliquant des espèces à un nombre pair d'atomes de carbone sans passer par le naphtalène. Selon ces auteurs, les premiers précurseurs des HAP sont le 1,3-butadiène et le radical phényle qui, après cyclisation, forment deux cycles en C 10 ou C 9 respectivement par élimination d'un atome d'hydrogène H ou d'un groupement méthyle :…”

Section: -P12unclassified

Croissance des HAP et des suies et transition phase gaz-phase solide dans les processus de combustion

Desgroux

Bakali

Mercier

2011

EPJ Web of Conferences

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Abstract. This article is addressed to a scientific community familiar to astrophysics, and most researchers are not familiar with combustion science. Thus the goal is to provide a basic understanding of "the flame" and the different steps that lead to soot particle formation in conditions that are generally close to atmospheric pressure and high temperature, i.e. in conditions far from those encountered in most astrophysical media. Some experimental techniques of sooty flame investigations will also be introduced. The main aim is to outline the concepts and the tools of combustion science to facilitate fruitful scientific exchanges between two communities that are motivated by the understanding of the formation and evolution of PAHs and soot-like particles, in completely different environments. It should be noted that the description does not pretend to be exhaustive at all and certain theoretical and experimental approaches are not described nor even mentioned.Résumé. Cet article s'adresse à une communauté «astrophysique» non familière avec la combustion. Il a pour but de donner quelques bases permettant de comprendre «la flamme» et les étapes chimiques principales conduisant à la formation de particules de suie dans un milieu généralement à pression atmosphérique et haute température, c'est-à-dire dans des conditions de pression et température très éloignées de celles rencontrées dans le milieu interstellaire. Certaines méthodes expérimentales d'investigation de flammes suitées sont également présentées. L'objectif étant de pouvoir jeter des ponts entre deux communautés éloignées mais rassemblées par un même intérêt pour les hydrocarbures aromatiques polycycliques et les particules de suie. Il est clair que la présentation qui est faite ici est très succincte et qu'elle fait l'impasse sur certaines théories, approches, méthodes expérimentales. . .

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Quantum Chemistry Investigation of Key Reactions Involved in the Formation of Naphthalene and Indene

Cited by 54 publications

References 32 publications

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis

Analysis of Some Reaction Pathways Active during Cyclopentadiene Pyrolysis

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

Croissance des HAP et des suies et transition phase gaz-phase solide dans les processus de combustion

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