Analytical potential energy surface for the NH3+HNH2+H2 reaction: Application of variational transition-state theory and analysis of the equilibrium constants and kinetic isotope effects using curvilinear and rectilinear coordinates J. Chem. Phys. 106, 4013 (1997) product ions, respectively. The cross sections for both reactions were found to increase with decreasing collision energy, E coll , in the range 8 μeV < E coll < 20 meV. The measured rate constant exhibits a curvature in a log(k)-log(E coll ) plot from which it is concluded that the Langevin capture model does not properly describe the Ne * + NH 3 reaction in the entire range of collision energies covered here. Calculations based on multichannel quantum defect theory were performed to reproduce and interpret the experimental results. Good agreement was obtained by including long range van der Waals interactions combined with a 6-12 Lennard-Jones potential. The branching ratio between the two reactive channels, =, is relatively constant, ≈ 0.3, in the entire collision energy range studied here. Possible reasons for this observation are discussed and rationalized in terms of relative time scales of the reactant approach and the molecular rotation. Isotopic differences between the Ne * + NH 3 and Ne * + ND 3 reactions are small, as suggested by nearly equal branching ratios and cross sections for the two reactions. © 2014 AIP Publishing LLC.

Modern computational methods have become so powerful for predicting the outcome for the H + H2 → H2 + H bimolecular exchange reaction that it might seem further experiments are not needed. Nevertheless, experiments have led the way to cause theorists to look more deeply into this simplest of all chemical reactions. The findings are less simple.

Resonances are among the clearest quantum mechanical signatures of scattering processes. Previously, shape resonances and Feshbach resonances have been observed in inelastic and reactive collisions involving atoms or diatomic molecules. Structure in the integral cross section has been observed in a handful of elastic collisions involving polyatomic molecules. The present paper presents the observation of shape resonances in the reactive scattering of a polyatomic molecule, NH3. A merged-beam study of the gas phase He((3)S1) + NH3 Penning ionization reaction dynamics is described in the collision energy range 3.3 μeV < Ecoll < 10 meV. In this energy range, the reaction rate is governed by long-range attraction. Peaks in the integral cross section are observed at collision energies of 1.8 meV and 7.3 meV and are assigned to ℓ = 15,16 and ℓ = 20,21 partial wave resonances, respectively. The experimental results are well reproduced by theoretical calculations with the short-range reaction probability Psr = 0.035. No clear signature of the orbiting resonances is visible in the branching ratio between NH3 (+) and NH2 (+) formation.

The field of cold molecules has become an important source of new insight in fundamental chemistry and molecular physics. High-resolution spectroscopy benefits from translationally and internally cold molecules by increased interaction times and reduced spectral congestion. Completely new effects in scattering dynamics become accessible with cold and controlled molecules. Many of these experiments use molecular beams as a starting point for the generation of molecular samples. This review gives an overview of methods to produce beams of cold molecules, starting from supersonic expansions or effusive sources, and provides examples of applications in spectroscopy and molecular dynamics studies.

Interferences are genuine quantum phenomena that appear whenever two seemingly distinct classical trajectories lead to the same outcome. They are common in elastic scattering but are seldom observable in chemical reactions. Here we report experimental measurements of the state-to-state angular distribution for the H + D2 reaction using the 'photoloc' technique. For products in low rotational and vibrational states, a characteristic oscillation pattern governs backward scattering. The comparison between the experiments, rigorous quantum calculations and classical trajectories on an accurate potential energy surface allows us to trace the origin of that structure to the quantum interference between different quasiclassical mechanisms, a phenomenon analogous to that observed in the double-slit experiment.