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Register a new userQuantum nature of molecular vibrational quenching: Water - molecular hydrogen collisions
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Laurent Wiesenfeld
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The relative orientation of colliding molecules plays a key role in determining the rates of chemical processes. Here we examine in detail a prototypical example: rotational quenching of HD in cold collisions with H2. We show that the rotational quenching rate from j=2 -> 0, in the v=1 vibrational level, can be maximized by aligning the HD along the collision axis and can be minimized by aligning the HD at the so called magic angle. This follows from quite general helicity considerations and suggests that quenching rates for other similar systems can also be controlled in this manner.
Supernova (SN) 1987A is the only young SN in which H_2 has been detected in the ejecta. The properties of the H_2 are important for understanding the explosion and the ejecta chemistry. Here, we present new VLT/SINFONI observations of H_2 in SN 1987A, focussing on the 2.12 mu m (1,0)S(1) line. We find that the 3D emissivity is dominated by a single clump in the southern ejecta, with weaker emission being present in the north along the plane of the circumstellar ring. The lowest observed velocities are in the range 400-800 km/s, in agreement with previous limits on inward mixing of H. The brightest regions of H_2 coincide with faint regions of Halpha, which can be explained by Halpha being powered by X-ray emission from the ring, while the H_2 is powered by 44Ti. A comparison with ALMA observations of other molecules and dust shows that the brightest regions of H_2, CO and SiO occupy different parts of the inner ejecta and that the brightest H_2 clump coincides with a region of very weak dust emission. The latter is consistent with theoretical predictions that the H_2 should form in the gas phase rather than on dust grains.
Theoretical cross sections for the pressure broadening by hydrogen of rotational transitions of water are compared to the latest available measurements in the temperature range 65-220 K. A high accuracy interaction potential is employed in a full close coupling calculation. A good agreement with experiment is observed above ~80 K while the sharp drop observed experimentally at lower temperatures is not predicted by our calculations. Possible explanations for this discrepancy include the failure of the impact approximation and the possible role of ortho-to-para conversion of H2.
We investigated the behavior of H$_2$, main constituent of the gas phase in dense clouds, after collision with amorphous solid water (ASW) surfaces, one of the most abundant chemical species of interstellar ices. We developed a general framework to study the adsorption dynamics of light species on interstellar ices. We provide binding energies and their distribution, sticking probabilities for incident energies between 1 meV and 60 meV, and thermal sticking coefficients between 10 and 300 K for surface temperatures from 10 to 110 K. We found that the sticking probability depends strongly on the adsorbate kinetic energy and the surface temperature, but hardly on the angle of incidence. We observed finite sticking probabilities above the thermal desorption temperature. Adsorption and thermal desorption should be considered as separate events with separate time scales. Laboratory results for these species have shown a gap in the trends attributed to the differently employed experimental techniques. Our results complement observations and extend them, increasing the range of gas temperatures under consideration. We plan to employ our method to study a variety of adsorbates, including radical and charged species.
For a small fraction of hot CO2 molecules immersed in a liquid-phase CO2 thermal bath, classical cavity molecular dynamics simulations show that forming collective vibrational strong coupling (VSC) between the C=O asymmetric stretch of CO2 molecules and a cavity mode accelerates hot-molecule relaxation. The physical mechanism underlying this acceleration is the fact that polaritons, especially the lower polariton, can be transiently excited during the nonequilibrium process, which facilitates intermolecular vibrational energy transfer. The VSC effects on these rates (i) resonantly depend on the cavity mode detuning, (ii) cooperatively depend on molecular concentration or Rabi splitting, and (iii) collectively scale with the number of hot molecules, which is similar to Dickes superradiance. For larger cavity volumes, due to a balance between this superradiant-like behavior and a smaller light-matter coupling, the total VSC effect on relaxation rates can scale slower than $1/N$, and the average VSC effect per molecule can remain meaningful for up to $N sim10^4$ molecules forming VSC. Moreover, we find that the transiently excited lower polariton prefers to relax by transferring its energy to the tail of the molecular energy distribution rather than equally distributing it to all thermal molecules. Finally, we highlight the similarities of parameter dependence between the current finding with VSC catalysis observed in Fabry-Perot microcavities.
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