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Register a new userPhotodissociation of small carbonaceous molecules of astrophysical interest
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Added by
Ewine F. van Dishoeck
Publication date
2008
fields
Physics
and research's language is
English
Authors
M.C. van Hemert
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Astronomical observations have shown that small carbonaceous molecules can persist in interstellar clouds exposed to intense ultraviolet radiation. Current astrochemical models lack quantitative information on photodissociation rates in order to interpret these data. We here present ab initio multi-reference configuration-interaction calculations of the vertical excitation energies, transition dipole moments and oscillator strengths for a number of astrophysically relevant molecules: C3, C4, C2H, l- and c-C3H, l- and c-C3H2, HC3H, l-C4H and l-C5H. Highly excited states up to the 9th root of each symmetry are computed, and several new states with large oscillator strengths are found below the ionization potentials. These data are used to calculate upper limits on photodissociation rates in the unattenuated interstellar radiation field by assuming that all absorptions above the dissociation limit lead to dissociation.
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Photodissociation is the dominant removal process of molecules in any region exposed to intense ultraviolet (UV) radiation. This includes diffuse and translucent interstellar clouds, dense photon-dominated regions, high velocity shocks, the surface layers of protoplanetary disks, and cometary and exoplanetary atmospheres. The rate of photodissociation depends on the cross sections for absorption into a range of excited electronic states, as well as on the intensity and shape of the radiation field at each position into the region of interest. Thus, an acccurate determination of the photodissociation rate of even a simple molecule like water or carbon monoxide involves many detailed considerations ranging from its electronic structure to its dissociation dynamics and the specifics of the radiation field that the molecule is exposed to. In this review chapter, each of these steps in determining photodissociation rates is discussed systematically and examples are provided.
Photodissociation of a molecule produces a spatial distribution of photofragments determined by the molecular structure and the characteristics of the dissociating light. Performing this basic chemical reaction at ultracold temperatures allows its quantum mechanical features to dominate. In this regime, weak applied fields can be used to control the reaction. Here, we photodissociate ultracold diatomic strontium in magnetic fields below 10 G and observe striking changes in photofragment angular distributions. The observations are in excellent qualitative agreement with a multichannel quantum chemistry model that includes nonadiabatic effects and predicts strong mixing of partial waves in the photofragment energy continuum. The experiment is enabled by precise quantum-state control of the molecules.
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