Theoretical Spectroscopic Study of Two Ketones of Atmospheric Interest: Methyl Glyoxal (CH3COCHO) and Methyl Vinyl Ketone (CH3COCH═CH2)

Two ketones of atmospheric interest, methyl glyoxal and methyl vinyl ketone, are studied using explicitly correlated coupled cluster theory and core-valence correlationconsistent basis sets. The work focuses on the far-infrared region. At the employed level of theory, the rotational constants can be determined to within a few megahertz of the experimental data. Both molecules present two conformers, trans/cis and antiperiplanar (Ap)/ synperiplanar (Sp), respectively. trans-Methyl glyoxal and Ap-methyl vinyl ketone are the preferred structures. cis-Methyl glyoxal is a secondary minimum of very low stability, which justifies the unavailability of experimental data in this form. In methyl vinyl ketone, the two conformers are almost isoenergetic, but the interconversion implies a relatively high torsional barrier of 1798 cm-1. A very low methyl torsional barrier was estimated for trans-methyl glyoxal (V3 = 273.6 cm-1). Barriers of 429.6 and 380.7 cm-1 were computed for Ap- and Sp-methyl vinyl ketone. Vibrational second-order perturbation theory was applied to determine the rovibrational parameters. The far-infrared region was explored using a variational procedure of reduced dimensionality. For trans-methyl glyoxal, the ground vibrational state was estimated to split by 0.067 cm-1, and the two low excited energy levels (1 0) and (0 1) were found to lie at 89.588 cm-1/88.683 cm-1 (A2/E) and 124.636 cm-1/123.785 cm-1 (A2/E). For Ap- and Sp-methyl vinyl ketone, the ground vibrational state splittings were estimated to be 0.008 and 0.017 cm-1, respectively.This project received funding from the European Union’s Horizon 2020 Research and Innovation Programme under Marie Skłodowska-Curie Grant Agreement 872081. The authors acknowledge the National Plan for Science, Technology and Innovation (MAARIFAH), King Abdulaziz City for Science and Technology, Kingdom of Saudi Arabia (Award 0061-001- 01-17-2) and the Ministerio de Ciencia, Innovación y Universidades of Spain (Grants EIN2019-103072, PID2020- 112887GB-I00, PID2019-104002GB-C21, and ERDF A Way of Making Europe, by the European Union Next Generation EU/ PRTR). The authors acknowledge CTI (CSIC) and CESGA and the Red Española de Computación for Grants AECT-2020- 2-0008 and RES-AECT-2020-3-0011 for computing facilities

Accurate spectroscopic characterization of ethyl mercaptan and dimethyl sufide isotopologues : a rute toward their astrophysical detection

Using state-of-the-art computational methodologies, we predict a set of reliable rotational and torsional parameters for ethyl mercaptan and dimethyl sulfide monosubstituted isotopologues. This includes rotational, quartic, and sextic centrifugal-distortion constants, torsional levels, and torsional splittings. The accuracy of the present data was assessed from a comparison to the available experimental data. Generally, our computed parameters should help in the characterization and the identification of these organo-sulfur molecules in laboratory settings and in the interstellar medium.This research was supported by a Marie Curie International Research Staff Exchange Scheme Fellowship within the 7th European Community Framework Program under grant No. PIRSES-GA-2012-31754, the COST Action CM1002 CODECS, and the FIS2011-28738-C02-02 project (MINECO, Spain). In Bologna, this work was supported by MIUR (PRIN 2012 funds under the project "STAR: Spectroscopic and computational Techniques for Astrophysical and atmospheric Research") and by the University of Bologna (RFO funds). M.L.S., M.H., and M.A.M. acknowledge the Deanship of Scientific Research at King Saud University for its funding through the Research Group RGP-VPP-333

The first microsolvation step for furans : new experiments and benchmarking strategies

The site-specific first microsolvation step of furan and some of its derivatives with methanol is explored to benchmark the ability of quantum-chemical methods to describe the structure, energetics, and vibrational spectrum at low temperature. Infrared and microwave spectra in supersonic jet expansions are used to quantify the docking preference and some relevant quantum states of the model complexes. Microwave spectroscopy strictly rules out in-plane docking of methanol as opposed to the top coordination of the aromatic ring. Contrasting comparison strategies, which emphasize either the experimental or the theoretical input, are explored. Within the harmonic approximation, only a few composite computational approaches are able to achieve a satisfactory performance. Deuteration experiments suggest that the harmonic treatment itself is largely justified for the zero-point energy, likely and by design due to the systematic cancellation of important anharmonic contributions between the docking variants. Therefore, discrepancies between experiment and theory for the isomer abundance are tentatively assigned to electronic structure deficiencies, but uncertainties remain on the nuclear dynamics side. Attempts to include anharmonic contributions indicate that for systems of this size, a uniform treatment of anharmonicity with systematically improved performance is not yet in sight

The furan microsolvation blind challenge for quantum chemical methods: First steps

© 2018 Author(s). Herein we present the results of a blind challenge to quantum chemical methods in the calculation of dimerization preferences in the low temperature gas phase. The target of study was the first step of the microsolvation of furan, 2-methylfuran and 2,5-dimethylfuran with methanol. The dimers were investigated through IR spectroscopy of a supersonic jet expansion. From the measured bands, it was possible to identify a persistent hydrogen bonding OH-O motif in the predominant species. From the presence of another band, which can be attributed to an OH-π interaction, we were able to assert that the energy gap between the two types of dimers should be less than or close to 1 kJ/mol across the series. These values served as a first evaluation ruler for the 12 entries featured in the challenge. A tentative stricter evaluation of the challenge results is also carried out, combining theoretical and experimental results in order to define a smaller error bar. The process was carried out in a double-blind fashion, with both theory and experimental groups unaware of the results on the other side, with the exception of the 2,5-dimethylfuran system which was featured in an earlier publication

Al(+V) compounds in gas phase: metastable AlO³⁺ trication

We use post Hartree–Fock advanced electronic structure computations to investigate the lowest electronic states of the AlO3+ trication. These computations confirm the existence of metastable AlO3+ ions in gas phase. At least three electronic states (13Π, 11Δ, 11Σ+) with potential wells are identified. These potential wells have depths of several hundreds of meV, which are deep enough to support several rovibrational levels where this trication may be found. Besides, we estimate the adiabatic triple ionisation energy of AlO at ∼55 eV. Furthermore, the current confirmation of the meta-stability of AlO3+ in gas phase should motivate the search for this aluminium oxide with Al(+V) in liquids and in solid state, in particular at high-pressure/high-temperature phases of alumina polymorphs and of aluminosilicates.</p

Characterization of the electronic states of the biological relevant SSNO molecule

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HNS + and HSN + cations: Electronic states, spin-rovibronic spectroscopy with planetary and biological implications

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Toward the laboratory identification of [O,N,S,S] isomers: Implications for biological NO chemistry

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‘Electronic and Vibrational Spectroscopy of CsS’

International audienceUsing multi configurational ab initio methodologies, we compute the potential energy curves (PECs) of the lowest electronic states of the diatomic CsS. These computations are performed using internally contracted multi reference interaction configuration including Davidson correction (MRCI+Q) with and without considering spin-orbit effects. The shapes of the PECs are governed by the interactions between the two ionic states, 2+ and 2, correlating at large internuclear separations (RCsS) to the first ionic dissociation limit and the other electronic states correlating to the three lowest neutral dissociation limits. Computations show the importance of considering large amount of electron correlation for the accurate description of the PECs and spectroscopy of this molecular system. As expected, these PECs are also strongly affected by the spin-orbit interaction. For the bound states, we report a set of spectroscopic parameters including equilibrium distances, dissociation energies, vibrational and rotational constants. The effects of spin-orbit-induced changes on these parameters are also discussed. Moreover, we show that the 22 state presents a “bowl” potential with a rather flat region extending to large RCsS distances. After being promoted to this state, wavepackets should undergo strong oscillations, similar to those observed by Zewail and co-workers for the NaI molecule. These should provide information on the shape of the PEC for the 22 state and also on the couplings between this and the neighbouring states

Theoretical investigation of the long-lived metastable AlO2+ dication in gas phase

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