Insights into the non-covalent interactions of hydrogen sulfide with fenchol and fenchone from a gas-phase rotational study.

The gas-phase non-covalent interactions in the endo-fenchol-H2S and fenchone-H2S complexes have been unveiled using rotational spectroscopy in a supersonic jet expansion and quantum chemical calculations. In endo-fenchol, the hydrogen bond HSH⋯OH together with dispersive interactions stabilizes the system. In fenchone, the weak interaction HSH⋯OC allows an internal dynamic of H2S.

Gas-phase hydration of nopinone: the interplay between theoretical methods and experiments unveils the conformational landscape.

The structure of microsolvated nopinone formed in the supersonic jet expansion is investigated in the gas phase. The rotational spectra of nopinone(H2O)n (n = 1, 2, 3) were analysed by means of Fourier transform microwave spectroscopy. In the present study, three monohydrates, two dihydrates and two trihydrates were observed and characterized. The observed structures are the lowest energy conformers predicted by quantum chemical calculations. In all the observed hydrates of nopinone, water was found to be linked to the ketone group (C[double bond, length as m-dash]O) with a strong hydrogen bond (ONOPHW) and finishing with a dispersive one (OWHNOP). The structure of nopinone was found to alter the structure of water dimer and water trimer, which make nopinone be surrounded with a chain of water molecules. A remarkable decrease in the H-bonding length was observed when the number of attached water molecules is increased. Different DFT and ab initio calculations at the equilibrium structure allowed the identification of the observed conformers. Evaluation of the B3LYP-D3 and ωB97X-D results revealed deficiencies in reproducing the structure of one observed monohydrated structure while MP2 and M06-2X reproduce all the three observed structures. A comparison with similar bicyclic ketones highlights how a small change in the bicyclic ring leads to different effects in the microsolvation of biogenic VOCs. This study presents the first step of molecular aggregation to understand the atmospheric formation of aerosols at the molecular scale.

Conformational changes in hydroxyl functional groups upon hydration: the case study of endo fenchol.

The hydration of endo-fenchol has been studied in the gas phase using a combination of Fourier transform microwave spectroscopy coupled to a supersonic jet expansion and theoretical calculations in the 2 to 20 GHz range. An endo-fencholwater complex was observed. Multi-isotopic substitutions of deuterated species have also been studied in order to confirm the identity of the observed monohydrated endo-fenchol due to the flexibility of the OH group. Herein, the structure of the observed conformer was unveiled. Water induced an alteration in the arrangement of the hydroxyl group. The observed species is stabilized by a hydrogen bond between one water molecule and the highest energy conformer of endo-fenchol, which was not observed in our previous study of the fenchol monomer. This study highlights the flexibility of alcohol molecules and the effect of the strong (O-HO) and weak (C-HO) hydrogen bonds on the stabilization of the cluster with water.

Gas-phase kinetics of CH3CHO with OH radicals between 11.7 and 177.5 K.

Gas-phase reactions in the interstellar medium (ISM) are a source of molecules in this environment. The knowledge of the rate coefficient for neutral-neutral reactions as a function of temperature, k(T), is essential to improve astrochemical models. In this work, we have experimentally measured k(T) for the reaction between the OH radical and acetaldehyde, both present in many sources of the ISM. Laser techniques coupled to a CRESU system were used to perform the kinetic measurements. The obtained modified Arrhenius equation is k(T = 11.7-177.5 K) = (1.2 ± 0.2) × 10-11 (T/300 K)-(1.8±0.1) exp-{(28.7 ± 2.5)/T} cm3 molecule-1 s-1. The k(T) value of the title reaction has been measured for the first time below 60 K. No pressure dependence of k(T) was observed at ca. 21, 50, 64 and 106 K. Finally, a pure gas-phase model indicates that the title reaction could become the main CH3CO formation pathway in dark molecular clouds, assuming that CH3CO is the main reaction product at 10 K.

The gas phase structure of α-pinene, a main biogenic volatile organic compound.

The gas phase structure of the bicyclic atmospheric aerosol precursor α-pinene was investigated employing a combination of quantum chemical calculation and Fourier transform microwave spectroscopy coupled to a supersonic jet expansion. The very weak rotational spectra of the parent species and all singly substituted 13C in natural abundance have been identified, from 2 to 20 GHz, and fitted to Watson's Hamiltonian model. The rotational constants were used together with geometrical parameters from density functional theory and ab initio calculations to determine the rs, r0, and rm(1) structures of the skeleton, without any structural assumption in the fit concerning the heavy atoms. The double C=C bond was found to belong to a quasiplanar skeleton structure containing 6 carbon atoms. Comparison with solid phase structure is reported. The significant differences of α-pinene in gas phase and other gas phase bicyclic monoterpene structures (ß-pinene, nopinone, myrtenal, and bicyclo[3.1.1]heptane) are discussed.