Context.The methyl cation (CH3+) has recently been discovered in the interstellar medium through the detection of 7 μm (1400 cm−1) features toward the d203-506 protoplanetary disk by the JWST. Line-by-line spectroscopic assignments of these features, however, were unsuccessful due to complex intramolecular perturbations preventing a determination of the excitation and abundance of the species in that source. Aims.Comprehensive rovibrational assignments guided by theoretical and experimental laboratory techniques provide insight into the excitation mechanisms and chemistry of CH3+in d203-506. Methods.The rovibrational structure of CH3+was studied theoretically by a combination of coupled-cluster electronic structure theory and (quasi-)variational nuclear motion calculations. Two experimental techniques were used to confirm the rovibrational structure of CH3+:(1) infrared leak-out spectroscopy of the methyl cation, and (2) rotationally resolved photoelectron spectroscopy of the methyl radical (CH3). In (1), CH3+ions, produced by the electron impact dissociative ionization of methane, were injected into a 22-pole ion trap where they were probed by the pulses of infrared radiation from the FELIX free electron laser. In (2), neutral CH3, produced by CH3NO2pyrolysis in a molecular beam, was probed by pulsed-field ionization zero-kinetic-energy photoelectron spectroscopy. Results.The quantum chemical calculations performed in this study have enabled a comprehensive spectroscopic assignment of thev2+andv4+bands of CH3+detected by the JWST. The resulting spectroscopic constants and derived EinsteinAcoefficients fully reproduce both the infrared and photoelectron spectra and permit the rotational temperature of CH3+(T= 660 ± 80 K) in d203-506 to be derived. A beam-averaged column density of CH3+in this protoplanetary disk is also estimated.
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A spectroscopic investigation of the lowest electronic states of the I2+ cation as a candidate for detecting the time variation of fundamental constants
The four lowest Ω substates (X2Π3/2,g, X2Π1/2,g, A2Π3/2,u and A2Π1/2,u) of the cation have been studied by high-precision ab initio calculations in comparison with experimental high-resolution absorption spectra. The potential energy curves were calculated using the multi-reference configuration interaction (MRCI) method and Dirac method, respectively. Rovibrational levels of these electronic states were derived by solving the radial Schrödinger rovibrational equation. Molecular constants were obtained in fitting energy levels to a spectroscopic model. Using the fit spectroscopic constants and newly calculated transition dipole moment matrix elements, line strengths of vibronic bands in the A2Π3/2,u- X2Π3/2,g system, as well as Einstein A coefficients for 45 of these bands with ν′ = 11–19 and ν′′ = 1–5, have been derived. The Einstein A coefficients were used to compute radiative lifetimes of the ν′ = 11–19 vibrational levels of the A2Π3/2,u state. Enhancement factors for detecting the variation of the fine-structure constant (α) and the proton-to-electron mass ratio(µ) using transitions between nearly degenerate rovibronic levels of these low-lying states have been calculated.
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- Award ID(s):
- 1454825
- PAR ID:
- 10538973
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Journal of Molecular Spectroscopy
- Volume:
- 399
- Issue:
- C
- ISSN:
- 0022-2852
- Page Range / eLocation ID:
- 111873
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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