Quantum chemical and dynamical approaches to intra and intermolecular kinetics: The CnH2nO (n = 1, 2, 3) molecules

Elango, M.; Maciel, Glauciete S.; Lombardi, Andrea; Cavalli, Simonetta; Aquilanti, Vincenz̊o

doi:10.1002/qua.22791

Cited by 18 publications

(8 citation statements)

References 44 publications

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“…Propylene oxide, also referred as methyl oxirane, has continuously received particular attention in the literature due to its chiral nature and is of particular relevance to us in relationship with current chirality changing experiments by aligned molecular beams . Recent work in this laboratory concerned molecules containing peroxidic and persulfidic bonds, characterizing the effect of substituents, and specifically considering processes of chirality changing isomerization by torsion. − Our interest currently is about investigating systematically a sequence of other oxygen-containing organic molecules of general formula C n H 2 n O, where n = 1, 2, 3 . These molecules involve a series of decomposition and isomerization processes, which are the subject matter of many ongoing experimental research activities. − …”

Section: Introductionmentioning

confidence: 99%

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

et al. 2010

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Electronic structure calculations were carried out to study the various isomers of formula C(3)H(6)O, as a part of our current quantum chemical and dynamical approaches to intra- and intermolecular kinetics for the C(n)H(2n)O (n = 1, 2, 3) molecules. The usefulness of the GRRM (global reaction route mapping) program developed by Ohno and Maeda in predicting the structure of all isomers and of the transition states connecting them is fully exploited. All the isomers are identified as local minima on the MP2/CC-PVDZ potential energy surface. Acetone is the most stable isomer. In increasing order of stability the others are propanal, 2-propenol, 1-propenol, allyl alcohol, methyl vinyl ether, cyclopropanol, propylene oxide, and oxetane. Various isomerization paths connecting them are identified. All the transition states are fully characterized using intrinsic reaction coordinate calculations. The isomerization reactions may proceed through a single step or involve an intermediate species which is either a carbene or a diradical. Special attention is devoted to propylene oxide, a favorite molecule in current photochemical and stereodynamical studies because of its chiral nature. It is a rigid molecule, and chirality switching is found to be supported by its isomers. Two different chirality switching mechanisms which are assisted by propanal and allyl alcohol are presented.

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Section: Introductionmentioning

confidence: 99%

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

et al. 2010

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“…Related electronic structure and chirality conversion mechanisms have been reported Elango et al 2010Elango et al , 2011.…”

Section: Work In Progress: a Summarymentioning

confidence: 96%

Aligned molecular collisions and a stereodynamical mechanism for selective chirality

Aquilanti

Grossi

Lombardi

et al. 2011

Rend. Fis. Acc. Lincei

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Investigations of the stereodynamics of elementary processes provide the background for perspective demonstration of the manifestation of chiral effects in molecular collisions. Advances in experimental vacuum technology allow the generation of molecular beams containing oriented molecules. Here, we focus on collisional alignment, a molecular polarization phenomenon occurring in supersonic expansions of gaseous mixtures. The underlying physical mechanisms, relevant gas-phase experiments and molecular dynamics simulations are illustrated, with reference to applications of these tools to the study of elementary processes occurring both in homogeneous and in heterogeneous phases, and are discussed in view of their fundamental relevance and also of possible interest in an astrochemical, protobiological context.

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“…Many alternative choices are available for adopting a specific set of angular coordinates Ω, some of them lead to a compact analytic expression of the PES and an intuitive connection with the geometric properties of the system. [30][31][32][33][34][35][36] Compact expansions can be obtained in terms of special angular functions (i.e., hyperspherical harmonics [37][38][39][40][41][42][43][44][45][46][47] ).…”

Section: A Potential Energy Surfacementioning

confidence: 99%

Energy transfer upon collision of selectively excited CO2 molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows

Lombardi

Faginas-Lago

Pacifici

et al. 2015

The Journal of Chemical Physics

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Carbon dioxide molecules can store and release tens of kcal/mol upon collisions, and such an energy transfer strongly influences the energy disposal and the chemical processes in gases under the extreme conditions typical of plasmas and hypersonic flows. Moreover, the energy transfer involving CO2 characterizes the global dynamics of the Earth-atmosphere system and the energy balance of other planetary atmospheres. Contemporary developments in kinetic modeling of gaseous mixtures are connected to progress in the description of the energy transfer, and, in particular, the attempts to include non-equilibrium effects require to consider state-specific energy exchanges. A systematic study of the state-to-state vibrational energy transfer in CO2 + CO2 collisions is the focus of the present work, aided by a theoretical and computational tool based on quasiclassical trajectory simulations and an accurate full-dimension model of the intermolecular interactions. In this model, the accuracy of the description of the intermolecular forces (that determine the probability of energy transfer in molecular collisions) is enhanced by explicit account of the specific effects of the distortion of the CO2 structure due to vibrations. Results show that these effects are important for the energy transfer probabilities. Moreover, the role of rotational and vibrational degrees of freedom is found to be dominant in the energy exchange, while the average contribution of translations, under the temperature and energy conditions considered, is negligible. Remarkable is the fact that the intramolecular energy transfer only involves stretching and bending, unless one of the colliding molecules has an initial symmetric stretching quantum number greater than a threshold value estimated to be equal to 7.

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Quantum chemical and dynamical approaches to intra and intermolecular kinetics: The C_nH_2nO (n = 1, 2, 3) molecules

Cited by 18 publications

References 44 publications

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

Aligned molecular collisions and a stereodynamical mechanism for selective chirality

Energy transfer upon collision of selectively excited CO2 molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows

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Quantum chemical and dynamical approaches to intra and intermolecular kinetics: The CnH2nO (n = 1, 2, 3) molecules

Cited by 18 publications

References 44 publications

Quantum Chemistry of C3H6O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

Quantum Chemistry of C3H6O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

Aligned molecular collisions and a stereodynamical mechanism for selective chirality

Energy transfer upon collision of selectively excited CO2 molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows

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Quantum chemical and dynamical approaches to intra and intermolecular kinetics: The C_nH_2nO (n = 1, 2, 3) molecules

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms

Quantum Chemistry of C₃H₆O Molecules: Structure and Stability, Isomerization Pathways, and Chirality Changing Mechanisms