Subscribe to the gold package and get unlimited access to Shamra Academy
Register a new userObservation of correlated excitations in bimolecular collisions
57
0
0.0
(
0
)
Ask ChatGPT about the research
No Arabic abstract
Whereas collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum state-resolved bimolecular cross sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb -- much less intuitive understanding -- of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.
rate research
Read More
The semiclassical Wigner treatment of bimolecular collisions, proposed by Lee and Scully on a partly intuitive basis [J. Chem. Phys. 73, 2238 (1980)], is derived here from first principles. The derivation combines E. J. Hellers ideas [J. Chem. Phys. 62, 1544 (1975); 65, 1289 (1976); 75, 186 (1981)], the backward picture of molecular collisions [L. Bonnet, J. Chem. Phys. 133, 174108 (2010)] and the microreversibility principle.
Whereas atom-molecule collisions have been studied with complete quantum state resolution, interactions between two state-selected molecules have proven much harder to probe. Here, we report the measurement of state-resolved inelastic scattering cross sections for collisions between two open-shell molecules that are both prepared in a single quantum state. Stark-decelerated OH radicals were scattered with hexapole-focused NO radicals in a crossed beam configuration. Rotationally and spin-orbit inelastic scattering cross sections were measured on an absolute scale for collision energies between 70 and 300 cm$^{-1}$. These cross sections show fair agreement with quantum coupled-channels calculations using a set of coupled model potential energy surfaces based on ab initio calculations for the long-range non-adiabatic interactions and a simplistic short-range interaction. This comparison reveals the crucial role of electrostatic forces in complex molecular collision processes.
The transition states and dividing surfaces used to find rate constants for bimolecular reactions are shown to undergo qualitative changes, known as Morse bifurcations, and to exist for a large range of energies, not just immediately above the critical energy for first connection between reactants and products. Specifically, we consider capture between two molecules and the associated transition states for the case of non-zero angular momentum and general attitudes. The capture between an atom and a diatom, and then a general molecule are presented, providing concrete examples of Morse bifurcations of transition states and dividing surfaces. The reduction of the $n$-body systems representing the reactions is discussed and reviewed with comments on the difficulties associated with choosing appropriate charts and the global geometry of the reduced spaces.
We investigate the influence of a stochastically fluctuating step-barrier potential on bimolecular reaction rates by exact analytical theory and stochastic simulations. We demonstrate that the system exhibits a new resonant reaction behavior with rate enhancement if an appropriately defined fluctuation decay length is of the order of the system size. Importantly, we find that in the proximity of resonance the standard reciprocal additivity law for diffusion and surface reaction rates is violated due to the dynamical coupling of multiple kinetic processes. Together, these findings may have important repercussions on the correct interpretation of various kinetic reaction problems in complex systems, as, e.g., in biomolecular association or catalysis.
Femtochemistry techniques have been instrumental in accessing the short time scales necessary to probe transient intermediates in chemical reactions. Here we take the contrasting approach of prolonging the lifetime of an intermediate by preparing reactant molecules in their lowest ro-vibronic quantum state at ultralow temperatures, thereby drastically reducing the number of exit channels accessible upon their mutual collision. Using ionization spectroscopy and velocity-map imaging of a trapped gas of potassium-rubidium molecules at a temperature of 500~nK, we directly observe reactants, intermediates, and products of the reaction $^{40}$K$^{87}$Rb + $^{40}$K$^{87}$Rb $rightarrow$ K$_2$Rb$^*_2$ $rightarrow$ K$_2$ + Rb$_2$. Beyond observation of a long-lived energy-rich intermediate complex, this technique opens the door to further studies of quantum-state resolved reaction dynamics in the ultracold regime.
Log in to be able to interact and post comments
comments
Fetching comments
Sign in to be able to follow your search criteria
