Vibrational-state-specific self-relaxation rate constant. Measurements of highly vibrationally excited O2(ν = 19–28)

1993 ◽  
Vol 175 (1) ◽  
pp. 83-98 ◽  
Author(s):  
J.M. Price ◽  
J.A. Mack ◽  
C.A. Rogaski ◽  
A.M. Wodtke
2018 ◽  
Vol 612 ◽  
pp. A48 ◽  
Author(s):  
K. T. Wong ◽  
K. M. Menten ◽  
T. Kamiński ◽  
F. Wyrowski ◽  
J. H. Lacy ◽  
...  

Context. The circumstellar ammonia (NH3) chemistry in evolved stars is poorly understood. Previous observations and modelling showed that NH3 abundance in oxygen-rich stars is several orders of magnitude above that predicted by equilibrium chemistry.Aims. We would like to characterise the spatial distribution and excitation of NH3 in the oxygen-rich circumstellar envelopes (CSEs) of four diverse targets: IK Tau, VY CMa, OH 231.8+4.2, and IRC +10420. Methods. We observed NH3 emission from the ground state in the inversion transitions near 1.3 cm with the Very Large Array (VLA) and submillimetre rotational transitions with the Heterodyne Instrument for the Far-Infrared (HIFI) aboard Herschel Space Observatory from all four targets. For IK Tau and VY CMa, we observed NH3 rovibrational absorption lines in the ν2 band near 10.5 μm with the Texas Echelon Cross Echelle Spectrograph (TEXES) at the NASA Infrared Telescope Facility (IRTF). We also attempted to search for the rotational transition within the excited vibrational state (v2 = 1) near 2 mm with the IRAM 30m Telescope. Non-LTE radiative transfer modelling, including radiative pumping to the vibrational state, was carried out to derive the radial distribution of NH3 in the CSEs of these targets. Results. We detected NH3 inversion and rotational emission in all four targets. IK Tau and VY CMa show blueshifted absorption in the rovibrational spectra. We did not detect vibrationally excited rotational transition from IK Tau. Spatially resolved VLA images of IK Tau and IRC +10420 show clumpy emission structures; unresolved images of VY CMa and OH 231.8+4.2 indicate that the spatial-kinematic distribution of NH3 is similar to that of assorted molecules, such as SO and SO2, that exhibit localised and clumpy emission. Our modelling shows that the NH3 abundance relative to molecular hydrogen is generally of the order of 10−7, which is a few times lower than previous estimates that were made without considering radiative pumping and is at least ten times higher than that in the carbon-rich CSE of IRC +10216. NH3 in OH 231.8+4.2 and IRC +10420 is found to emit in gas denser than the ambient medium. Incidentally, we also derived a new period of IK Tau from its V-band light curve. Conclusions. NH3 is again detected in very high abundance in evolved stars, especially the oxygen-rich ones. Its emission mainly arises from localised spatial-kinematic structures that are probably denser than the ambient gas. Circumstellar shocks in the accelerated wind may contribute to the production of NH3. Future mid-infrared spectroscopy and radio imaging studies are necessary to constrain the radii and physical conditions of the formation regions of NH3.


The reaction between cyanogen radicals and oxygen has been studied and the rate constant for the reaction at room temperature found to be 4.6 × 10 12 ml. mole -1 s -1 . The reaction is predominantly CN+ O 2 → NCO + O, with a contribution of < 15 % from the reaction CN + O 2 → CO + NO. The nitric oxide produced in this reaction is vibrationally excited. In the presence of excess oxygen, ozone is produced in the reaction O + O 2 + M → O 2 + M, for which the rate constant is found to be 1.1 ± 0.6 × 10 8 l. 2 mole -2 s -1 . A new spectrum has been observed and is assigned to the molecules N 2 C 2 O or NCO 2 CN produced in the reaction CN+ NCO → N 2 C 2 O or CN + NCO 2 → NCO 2 CN.


A study of the flash photolysis of chlorine monoxide and of its photosensitized decomposition by chlorine and bromine has yielded rate constants for the reactions Cl + Cl 2 O → Cl 2 + ClO, k 1 = 4.1 x 10 8 l mol -1 s -1 , Br + Cl 2 O → BrCl + ClO, k 9 = 6.1 x 10 8 l mol -1 s -1 , ClO + Cl 2 O → ClO 2 + Cl 2 , k 3 = 2.6 x 10 5 l mol -1 s -1 , ClO + Cl 2 O → Cl 2 + O 2 + Cl, k 4 = 6.5 x 10 5 l mol -1 s -1 , 2ClO → Cl 2 + O 2 , k 2 = 2.8 x 10 7 l mol -1 s -1 . The quantum yield for the decomposition of chlorine monoxide was measured in each of the three systems and is quantitatively accounted for by the reactions given. The CIO free radical has been flash photolysed and the production of vibrationally excited oxygen in the reaction O + CIO → Cl + O* 2 ( v" ≼ 14), k 11 = 7.5 x 10 9 l mol -1 s -1 demonstrated. The same reaction is responsible for the production of O* 2 in the flash photo­lysis of Cl 2 O with radiation below ~ 300 nm. The relaxation of O* 2 by chlorine atoms is exceptionally efficient, with a rate constant for v" = 12 in excess of 2 x 10 9 l mol -1 s -1 . The corresponding rate constant for relaxation by Cl 2 O is < 10 8 l mol -1 s -1 .


2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yao Chang ◽  
Feng An ◽  
Zhichao Chen ◽  
Zijie Luo ◽  
Yarui Zhao ◽  
...  

AbstractVibrationally excited molecular hydrogen has been commonly observed in the dense photo-dominated regions (PDRs). It plays an important role in understanding the chemical evolution in the interstellar medium. Until recently, it was widely accepted that vibrational excitation of interstellar H2 was achieved by shock wave or far-ultraviolet fluorescence pumping. Here we show a further pathway to produce vibrationally excited H2 via the water photochemistry. The results indicate that the H2 fragments identified in the O(1S) + H2(X1Σg+) channel following vacuum ultraviolet (VUV) photodissociation of H2O in the wavelength range of λ = ~100-112 nm are vibrationally excited. In particular, more than 90% of H2(X) fragments populate in a vibrational state v = 3 at λ~112.81 nm. The abundance of water and VUV photons in the interstellar space suggests that the contributions of these vibrationally excited H2 from the water photochemistry could be significant and should be recognized in appropriate interstellar chemistry models.


2017 ◽  
Vol 609 ◽  
pp. A25 ◽  
Author(s):  
A. Baudry ◽  
E. M. L. Humphreys ◽  
F. Herpin ◽  
K. Torstensson ◽  
W. H. T. Vlemmings ◽  
...  

Context. Several rotational transitions of ortho- and para-water have been identified toward evolved stars in the ground vibrational state as well as in the first excited state of the bending mode (v2 = 1 in (0, 1, 0) state). In the latter vibrational state of water, the 658 GHz J = 11,0−10,1 rotational transition is often strong and seems to be widespread in late-type stars. Aims. Our main goals are to better characterize the nature of the 658 GHz emission, compare the velocity extent of the 658 GHz emission with SiO maser emission to help locate the water layers and, more generally, investigate the physical conditions prevailing in the excited water layers of evolved stars. Another goal is to identify new 658 GHz emission sources and contribute in showing that this emission is widespread in evolved stars. Methods. We have used the J = 11,0−10,1 rotational transition of water in the (0, 1, 0) vibrational state nearly 2400 K above the ground-state to trace some of the physical conditions of evolved stars. Eleven evolved stars were extracted from our mini-catalog of existing and potential 658 GHz sources for observations with the Atacama Pathfinder EXperiment (APEX) telescope equipped with the SEPIA Band 9 receiver. The 13CO J = 6−5 line at 661 GHz was placed in the same receiver sideband for simultaneous observation with the 658 GHz line of water. We have compared the ratio of these two lines to the same ratio derived from HIFI earlier observations to check for potential time variability in the 658 GHz line. We have compared the 658 GHz line properties with our H2O radiative transfer models in stars and we have compared the velocity ranges of the 658 GHz and SiO J = 2−1, v = 1 maser lines. Results. Eleven stars have been extracted from our catalog of known or potential 658 GHz evolved stars. All of them show 658 GHz emission with a peak flux density in the range ≈50–70 Jy (RU Hya and RT Eri) to ≈2000–3000 Jy (VY CMa and W Hya). Five Asymptotic Giant Branch (AGB) stars and one supergiant (AH Sco) are new detections. Three AGBs and one supergiant (VY CMa) exhibit relatively weak 13CO J = 6−5 line emission while o Ceti shows stronger 13CO emission. We have shown that the 658 GHz line is masing and we found that the 658 GHz velocity extent tends to be correlated with that of the SiO maser suggesting that both emission lines are excited in circumstellar layers close to the central star. Broad and stable line profiles are observed at 658 GHz. This could indicate maser saturation although we have tentatively provided first information on time variability at 658 GHz.


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