/pdf/studies-in-surface-science-and-catalysis-2ogdlcr44y.pdf

Studies in Surface Science and Catalysis

Journal of Chemical Physics, Vol. 36-37 : 1962年に発表されたレオロジー関連の論文

Journal of Physical Chemisry A: Editorial

Chemical understanding is driven by the experimental discovery of new compounds and reactivity, and is supported by theory and computation that provides detailed physical insight. While theoretical and computational studies have generally focused on specific processes or mechanistic hypotheses, recent methodological and computational advances harken the advent of their principal role in discovery. Here we report the development and application of the ab initio nanoreactor – a highly accelerated, first-principles molecular dynamics simulation of chemical reactions that discovers new molecules and mechanisms without preordained reaction coordinates or elementary steps. Using the nanoreactor we show new pathways for glycine synthesis from primitive compounds proposed to exist on the early Earth, providing new insight into the classic Urey-Miller experiment. These results highlight the emergence of theoretical and computational chemistry as a tool for discovery in addition to its traditional role of interpreting experimental findings.

/pdf/discovering-chemistry-with-an-ab-initio-nanoreactor-1v1zz669b4.pdf

Discovering chemistry with an ab initio nanoreactor

Proceedings of the Combustion Institute

https://hal.archives-ouvertes.fr/hal-01676234/document

Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane

Transfer learning for solvation free energies: From quantum chemistry to experiments

The thermal decomposition of furfural is investigated experimentally and through theoretical calculations at the CBS-QB3 level of theory. Furfural is a major product observed during biomass pyrolysis, but despite its importance there are many speculations about the thermal decomposition channels of this compound. To address these open questions new experiments are performed in a jet-stirred reactor at atmospheric pressure and temperatures ranging from 900 to 1100 K with a furfural inlet mole fraction of 0.005 and He as diluent. The residence time is set to 2 s. The main products observed by GC analysis are CO, CO2, α-pyrone, furan, 3-furaldehyde, propyne, propadiene, acetylene, methane and benzene. Small amounts of other aromatics, e.g. toluene, styrene, benzaldehyde and phenol are observed as well. Theoretical calculations at the CBS-QB3 level are used to extend the furfural potential energy surface and to identify possible reaction pathways to the observed products. The unimolecular non-radical decomposition channel through α-pyrone as proposed in literature is confirmed as the main channel, but carbene pathways are found to make small contributions as well. Furthermore, pericyclic reactions are suggested to contribute to the molecular elimination of CO in open-chain molecules and Diels Alder reactions are found to be important for the formation of CO2 and aromatics. Finally, even radical chemistry initiated by homolytic scission of the approximately 380 kJ/mol strong C H bond in the furfural carbonyl group has a non-negligible influence.

/pdf/the-thermal-decomposition-of-furfural-molecular-chemistry-4rbel4oyjg.pdf

The thermal decomposition of furfural : molecular chemistry unraveled

https://hal.archives-ouvertes.fr/hal-01575555/document

Experimental and kinetic modeling study of the pyrolysis and oxidation of 1,5-hexadiene: The reactivity of allylic radicals and their role in the formation of aromatics

Florence Vermeire

Papers

Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane

Transfer learning for solvation free energies: From quantum chemistry to experiments

Experimental and modeling study of the pyrolysis and combustion of dimethoxymethane

The thermal decomposition of furfural : molecular chemistry unraveled

Experimental and kinetic modeling study of the pyrolysis and oxidation of 1,5-hexadiene: The reactivity of allylic radicals and their role in the formation of aromatics