New computational and experimental studies have been carried out for the MgCCH radical in its X2Σ+ state. Coupled cluster theory with single, double, and perturbative triples, CCSD(T), was used in conjunction with post-CCSD(T) and scalar relativistic additive corrections to compute vibrational quartic force fields for this molecule. From the quartic force fields, higher-order spectroscopic properties, including rotational constants, were obtained. In tandem, the five lowest energy rotational transitions for MgCCH, N = 1→0 through N = 5→4, were measured for the first time using Fourier transform microwave/millimeter wave methods in the frequency range 9 -50 GHz. The radical was created in the Discharge Assisted Laser Ablation Source (DALAS) developed in the Ziurys group. A combined fit of these data with previous millimeter direct absorption measurements have yielded the most accurate rotational constants for MgCCH to date. The computed principle rotational constant lies within 1.51-1.65 MHz of the experimental one, validating the computational approach. High-level theory was then applied to produce accurate rovibrational spectroscopic constants for MgCCH+, including a rotational constant of B0 = 5354.5–5359.5 MHz.. These new predictions will further the experimental study of MgCCH+, and aid in the low-temperature characterization of MgCCH, detected towards the circumstellar shell of IRC+10216, a carbon-rich star.
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The Ground State of KO Revisited: Millimeter and Submillimeter Spectrum of Potassium Oxide
The millimeter/sub-millimeter spectrum of the KO radical has been recorded in the frequency range 90–534 GHz using direct absorption methods. The radical was synthesized by reacting potassium vapor, produced with a Broida-type oven, with either N2O or O2 mixed in argon carrier gas. Twenty-seven rotational transitions of KO were measured, each exhibiting a doublet structure with a relatively small splitting (~100–200 MHz) that increased noticeably with frequency. A perturbation was apparent in the rotational lines at energies above ~120 cm-1, which was more prominent in one doublet component. The data were successfully fit with a Hund’s case (c) Hamiltonian, assuming that spectra arise from a 2Pi state, and rotational and effective lambda-doubling constants were determined. Higher order centrifugal distortion terms were needed to account for the perturbation. The spectra could also be fit as a 2S+ ground state, but less successfully, and the resulting rotational constant of B = 8235.4 MHz disagreed significantly with that predicted by theory. On the basis of the experimental data, the ground electronic state of KO has been assigned as 2Pi, although the 2S+ assignment cannot be entirely ruled out.
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- Award ID(s):
- 1907910
- PAR ID:
- 10203441
- Date Published:
- Journal Name:
- Physical chemistry chemical physics
- Volume:
- 21
- ISSN:
- 1463-9076
- Page Range / eLocation ID:
- 21960
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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