Chemistry

Reactivity: potential energy hypersurfaces


Example of the reaction coordinates

Example: reaction coordinates for the addition of water to propene

In the following, using the example of non-radical addition of water to propene, the Markovnikov and anti-Markovnikov rules, according to which the hydrogen atom should come to the hydrogen-rich carbon atom of the double bond, will be examined more closely. The videos below show the structural changes of the reaction complexes along the reaction coordinate during the formation of the Markovnikov product compared to the formation of the anti-Markovnikov product.

Compare the energetic position (Heat of Formation) of the transition states and end products in the formation of the Markovnikov and the Antimarkovnikov product! Which product is preferably formed under thermodynamic control, and which one could be obtained if the reaction is carried out under kinetic control?


Chemical reactivity on metal clusters in the gas phase driven by black body radiation †

We thank the EPSRC for financial support. A.K. thanks the Royal Society for financial support as part of a Newton International Fellowship.

Abstract

Gently taught: A blackbody radiation field provides enough excitation energy to drive the decomposition of nitrous oxide on isolated rhodium clusters. This gentlest of all photoexcitation techniques, which in many ways resembles blackbody radiation induced decay (BIRD), provides unique information about the barriers of the input channels for this important catalytic process.

Abstract

Chemical reactions in Rhn(N2O)m + Complexes in the gas phase have been observed, which are driven by absorption of black body radiation. The experiments were carried out under bumpless conditions in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The absorption of radiation in the mid-infrared range by the molecularly bound N2O units allows a small fraction of the cluster distribution, N2O decompose. This creates cluster oxides and releases molecular nitrogen. The decomposition of N2O competes with the desorption of the molecules. The branching relationships of the two processes show clear size effects that reflect differences in the relative barriers. The rate constant of the decay increases approximately linearly with the number of infrared chromophores. The experimental results are interpreted using calculated infrared absorption rates.

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