We study the barrierless and highly exothermic F + NH(3) and F + ND(3) abstraction reactions using quasiclassical trajectory calculations based on an analytical potential energy surface developed in our research group. The calculations correctly reproduce the experimental evidence that the vibrational fraction deposited into the DF product for the F + ND(3) reaction is greater than into HF for the F + NH(3) reaction and that the vibrational distribution is inverted in the HF(v') and the DF(v') products. Of special interest is that recent crossed-beam experiments reported by Yang and co-workers at 4.5 kcal mol(-1) are reproduced for both reactions, with a mainly forward symmetry associated with direct trajectories, and a small sideways-backward symmetry contribution associated with "nearly trapped" trajectories due to a "yo-yo" mechanism, different from the previously suggested mechanism of a long-lived complex.
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http://dx.doi.org/10.1021/jp208358x | DOI Listing |
Rev Sci Instrum
September 2024
Radboud University Nijmegen, Institute for Molecules and Materials, Heijendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.
In low-energy collisions between two dipolar molecules, the long-range dipole-dipole interaction plays an important role in the scattering dynamics. Merged beam configurations offer the lowest collision energies achievable, but they generally cannot be applied to most dipole-dipole systems as the electrodes used to merge one beam would deflect the other. This paper covers the design and implementation of a merged electrostatic guide whose geometry was numerically optimized for ND3-ND3 and ND3-NH3 collisions.
View Article and Find Full Text PDFChem Commun (Camb)
July 2024
Department of Chemical System Engineering, School of Engineering, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, Japan.
This study investigated the ammonia decomposition mechanism over Ru/CeO. Isotopic tests using ND revealed that the rate-determining step involves adsorbed nitrogen atoms on Ru. Moreover, an inverse kinetic isotope effect where ND decomposition was faster than NH was clearly observed.
View Article and Find Full Text PDFFaraday Discuss
August 2024
Department of Chemistry, University of California, Berkeley, CA 94720, USA.
The evaporation and scattering of ND from a dodecane flat liquid jet are investigated and the results are compared with previous studies on molecular beam scattering from liquid surfaces. Evaporation is well-described by a Maxwell-Boltzmann flux distribution with a cos angular distribution at the liquid temperature. Scattering experiments at = 28.
View Article and Find Full Text PDFJ Phys Chem A
October 2023
Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Lausanne CH-1015, Switzerland.
Despite its simplicity, the single-trajectory thawed Gaussian approximation has proven useful for calculating the vibrationally resolved electronic spectra of molecules with weakly anharmonic potential energy surfaces. Here, we show that the thawed Gaussian approximation can capture surprisingly well even more subtle observables, such as the isotope effects in the absorption spectra, and we demonstrate it on the four isotopologues of ammonia (NH, NDH, NDH, and ND). The differences in their computed spectra are due to the differences in the semiclassical trajectories followed by the four isotopologues, and the isotope effects─narrowing of the transition band and reduction of the peak spacing─are accurately described by this semiclassical method.
View Article and Find Full Text PDFJ Phys Chem Lett
September 2023
Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan.
Proton transfer is classified into two mechanisms: the Grotthuss (proton-relay) and vehicle mechanisms. It has been well studied on gas-phase proton transfer by a proton relay involving multiple molecules. However, a vehicle mechanism in which a single molecule transports a proton has rarely been reported.
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