Perfluorination of Aromatic Compounds Reinforce Their van der Waals Interactions with Rare Gases: The Rotational Spectrum of Pentafluoropyridine-Ne

The rotational spectrum of the pentafluoropyridine-Ne complex, generated in a supersonic jet, has been investigated using chirped-pulse microwave Fourier transform spectroscopy in the 2–8 GHz range. The spectra of the 20Ne and 22Ne species have been observed, and the rotational constants have been used to determine the structure of the complex. This structure, and those of the previously experimentally studied complexes benzene-Ne and pyridine-Ne, are an excellent benchmark for the theoretical calculations on these adducts. These complexes and hexafluorobenzene-Ne have been investigated at the CCSD/6-311++G(2d,p) level. The calculations reproduce the experimental structures well and show how the van der Waals complexes are stronger for the perfluorinated compound.

Attaching onto or Inserting into an Intramolecular Hydrogen Bond: Exploring and Controlling a Chirality-Dependent Dilemma for Alcohols

Prereactive complexes in noncovalent organocatalysis are sensitive to the relative chirality of the binding partners and to hydrogen bond isomerism. Both effects are present when a transiently chiral alcohol docks on a chiral α-hydroxy ester, turning such 1:1 complexes into elementary, non-reactive model systems for chirality induction in the gas phase. With the help of linear infrared and Raman spectroscopy in supersonic jet expansions, conformational preferences are investigated for benzyl alcohol in combination with methyl lactate, also exploring p-chlorination of the alcohol and the achiral homolog methyl glycolate to identify potential London dispersion and chirality effects on the energy sequence. Three of the four combinations prefer barrierless complexation via the hydroxy group of the ester (association). In contrast, the lightest complex shows predominantly insertion into the intramolecular hydrogen bond, like the analogous lactate and glycolate complexes of methanol. The experimental findings are rationalized with computations and a uniform helicality induction in the alcohol by the lactate is predicted, independent on insertion into or association with the internal lactate hydrogen bond. p-Chlorination of benzyl alcohol has a stabilizing effect on association, because the insertion motif prevents a close contact between the chlorine and the hydroxy ester. After simple anharmonicity and substitution corrections, the B3LYP-D3 approach offers a fairly systematic description of the known spectroscopic data on alcohol complexes with α-hydroxy esters.

Effect of flat wall length on decay and shock structure of a supersonic square wall jet

Experiments were conducted to find the effect of wall length on the decay behaviour and shock structure of a supersonic wall jet issuing from c-d nozzle of the square-shaped exit. A straight flat wall of width same as the side length of the square was attached to the lip of the nozzle such that the leading edge of the wall and the side of the square aligned properly which allowed the supersonic jet to graze past the flat wall. Experiments were conducted with five different wall lengths, that is, [Formula: see text] = 0.5, 1, 2, 4 and 8. Wall pressure measurements were made from leading edge to the trailing edge of the wall along its centreline. Schlieren flow visualization of the jet flow over the wall for the different wall lengths revealed the shock pattern and the effect of the wall length on the shock structure. The shock structure and jet deflection were significantly affected due to the presence of the wall. There was an upward jet deflection for [Formula: see text] up to [Formula: see text] whereas a downward jet deflection was observed for [Formula: see text]. Noticeable changes in the shock structure were observed for the wall lengths up to 2 D h. The wall length also significantly affected the jet decay characteristics and supersonic core length. Maximum enhancement in jet decay and maximum reduction in supersonic core length resulted when the wall length was [Formula: see text]. However, when the wall length was increased to [Formula: see text], there was a significant reduction in jet decay and a recovery of [Formula: see text]. Presence of wall always resulted a reduction in Lsc irrespective of wall length. The wall effect was to induce a more precipitous pressure drop closer to the nozzle exit, and a more gradual drop farther from it for [Formula: see text] > [Formula: see text].