DOI:10.1126/SCIENCE.1079294 - Corpus ID: 20959068
Carbon Tunneling from a Single Quantum State
@article{Zuev2003CarbonTF, title={Carbon Tunneling from a Single Quantum State}, author={Peter S. Zuev and Robert S. Sheridan and Titus V. Albu and Donald G. Truhlar and David A. Hrovat and Weston Thatcher Borden}, journal={Science}, year={2003}, volume={299}, pages={867 - 870}, url={https://api.semanticscholar.org/CorpusID:20959068}}- P. S. ZuevR. SheridanW. T. Borden
- Published inScience7 February 2003
- Chemistry, Physics
Calculations indicated that at this temperature the reaction proceeds from a single quantum state of the reactant so that the computed rate constant has achieved a temperature-independent limit.
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Real-Space Observation of Quantum Tunneling by a Carbon Atom: Flipping Reaction of Formaldehyde on Cu(110)
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The rate constant for carbon tunneling in the ring expansion of noradamantylmethylcarbene (1d) to 2-methyladamatene at T </~ 10 K is calculated to be lower by more than 8 orders of magnitude than the rate Constant for formation of 3-vinylnoradamantsane from 1d by hydrogen migration.
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These experimental findings are supported by calculations performed at the CASSCF and CASPT2 levels by using the small-curvature tunneling (SCT) approximation, which indicates that the reaction proceeds through quantum mechanical tunneling from the lowest vibrational level of the reactant.
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Using the tunneling-controlled reactivity of cyclopropylmethylcarbene, we demonstrate the viability of isotope-controlled selectivity (ICS), a novel control element of chemical reactivity where a…
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It is unequivocally shown that at cryogenic temperatures, the intersystem crossing occurs solely in the quantum tunneling regime, with weak coupling non-adiabatic transition state theory rate constants predicting a spontaneous reaction in fair agreement with experimental observations.
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