Theoretical spectroscopic study of acetyl (CH3CO), vinoxy (CH2CHO), and 1-methylvinoxy (CH3COCH2) radicals. Barrierless formation processes of acetone in the gas phase

Background: Acetone is present in the earth´s atmosphere and extra-terrestrially. The knowledge of its chemical history in these environments represents a challenge with important implications for global tropospheric chemistry and astrochemistry. The results of a search for efficient barrierless pathways producing acetone from radicals in the gas phase are described in this paper. The spectroscopic properties of radicals needed for their experimental detection are provided. Methods: The reactants were acetone fragments of low stability and small species containing C, O and H atoms. Two exergonic bimolecular addition reactions involving the radicals CH3, CH3CO, and CH3COCH2, were found to be competitive according to the kinetic rates calculated at different temperatures. An extensive spectroscopic study of the radicals CH3COCH2 and CH3CO, as well as the CH2CHO isomer, was performed. Rovibrational parameters, anharmonic vibrational transitions, and excitations to the low-lying excited states are provided. For this purpose, RCCSD(T)-F12 and MRCI/CASSCF calculations were performed. In addition, since all the species presented non-rigid properties, a variational procedure of reduced dimensionality was employed to explore the far infrared region. Results: The internal rotation barriers were determined to be V3=143.7 cm-1 (CH3CO), V2=3838.7 cm-1 (CH2CHO) and V3=161.4 cm-1 and V2=2727.5 cm-1 (CH3COCH2).The splitting of the ground vibrational state due to the torsional barrier have been computed to be 2.997 cm-1, 0.0 cm-1, and 0.320 cm-1, for CH3CO, CH2CHO, and CH3COCH2, respectively. Conclusions: Two addition reactions, H+CH3COCH2 and CH3+CH3CO, could be considered barrierless formation processes of acetone after considering all the possible formation routes, starting from 58 selected reactants, which are fragments of the molecule. The spectroscopic study of the radicals involved in the formation processes present non-rigidity. The interconversion of their equilibrium geometries has important spectroscopic effects on CH3CO and CH3COCH2, but is negligible for CH2CHO.

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Broadband spectroscopy of astrophysical ice analogues

Astronomy and Astrophysics ◽

10.1051/0004-6361/201935619 ◽

2019 ◽

Vol 629 ◽

pp. A112 ◽

Cited By ~ 8

Author(s):

B. M. Giuliano ◽

A. A. Gavdush ◽

B. Müller ◽

K. I. Zaytsev ◽

T. Grassi ◽

...

Keyword(s):

Refractive Index ◽

Optical Properties ◽

Time Domain ◽

Complex Refractive Index ◽

Far Infrared ◽

Infrared Region ◽

Thz Radiation ◽

The Real ◽

Thz Range ◽

The Time Domain

Context. Reliable, directly measured optical properties of astrophysical ice analogues in the infrared and terahertz (THz) range are missing from the literature. These parameters are of great importance to model the dust continuum radiative transfer in dense and cold regions, where thick ice mantles are present, and are necessary for the interpretation of future observations planned in the far-infrared region. Aims. Coherent THz radiation allows for direct measurement of the complex dielectric function (refractive index) of astrophysically relevant ice species in the THz range. Methods. We recorded the time-domain waveforms and the frequency-domain spectra of reference samples of CO ice, deposited at a temperature of 28.5 K and annealed to 33 K at different thicknesses. We developed a new algorithm to reconstruct the real and imaginary parts of the refractive index from the time-domain THz data. Results. The complex refractive index in the wavelength range 1 mm–150 μm (0.3–2.0 THz) was determined for the studied ice samples, and this index was compared with available data found in the literature. Conclusions. The developed algorithm of reconstructing the real and imaginary parts of the refractive index from the time-domain THz data enables us, for the first time, to determine the optical properties of astrophysical ice analogues without using the Kramers–Kronig relations. The obtained data provide a benchmark to interpret the observational data from current ground-based facilities as well as future space telescope missions, and we used these data to estimate the opacities of the dust grains in presence of CO ice mantles.

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Temperature-Dependent Stimulated Emission Cross-Section in Nd3+:YLF Crystal

Materials ◽

10.3390/ma14020431 ◽

2021 ◽

Vol 14 (2) ◽

pp. 431

Author(s):

Giorgio Turri ◽

Scott Webster ◽

Michael Bass ◽

Alessandra Toncelli

Keyword(s):

Cross Section ◽

Cross Sections ◽

Room Temperature ◽

Radiative Decay ◽

Emission Cross Section ◽

Spectroscopic Properties ◽

Stimulated Emission ◽

Different Temperatures ◽

Stimulated Emission Cross Section ◽

Semi Empirical

Spectroscopic properties of neodymium-doped yttrium lithium fluoride were measured at different temperatures from 35 K to 350 K in specimens with 1 at% Nd3+ concentration. The absorption spectrum was measured at room temperature from 400 to 900 nm. The decay dynamics of the 4F3/2 multiplet was investigated by measuring the fluorescence lifetime as a function of the sample temperature, and the radiative decay time was derived by extrapolation to 0 K. The stimulated-emission cross-sections of the transitions from the 4F3/2 to the 4I9/2, 4I11/2, and 4I13/2 levels were obtained from the fluorescence spectrum measured at different temperatures, using the Aull–Jenssen technique. The results show consistency with most results previously published at room temperature, extending them over a broader range of temperatures. A semi-empirical formula for the magnitude of the stimulated-emission cross-section as a function of temperature in the 250 K to 350 K temperature range, is presented for the most intense transitions to the 4I11/2 and 4I13/2 levels.

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