We characterize the double-faced nature of hydrogen bonding in hydroxy-functionalized ionic liquids by means of neutron diffraction with isotopic substitution (NDIS), molecular dynamics (MD) simulations,and quantum chemical calculations.N DIS data are fit using the empirical potential structure refinement technique (EPSR) to elucidate the nearest neighbor H···O and O···O pair distribution functions for hydrogen bonds between ions of opposite charge and the same charge.D espite the presence of repulsive Coulomb forces,t he cation-cation interaction is stronger than the cation-anion interaction. We compare the hydrogen-bond geometries of both "doubly charged hydrogen bonds" with those reported for molecular liquids,such as water and alcohols.Incombination, the NDIS measurements and MD simulations reveal the subtle balance between the two types of hydrogen bonds:T he small transition enthalpysuggests that the elusive like-charge attraction is almost competitive with conventional ion-pair formation.
We present results of a combined vacuum ultraviolet (VUV) and infrared (IR) photoabsorption study of amorphous benzene : water mixtures and layers to investigate the benzene-water interaction in the solid phase. VUV spectra of 1 : 1, 1 : 10 and 1 : 100 benzene : water mixtures at 24 K reveal a concentration dependent shift in the energies of the 1B2u, 1B1u and 1E1u electronic states of benzene. All the electronic bands blueshift from pure amorphous benzene towards gas phase energies with increasing water concentration. IR results reveal a strong dOH-π benzene-water interaction via the dangling OH stretch of water with the delocalised π system of the benzene molecule. Although this interaction influences the electronic states of benzene with the benzene-water interaction causing a redshift in the electronic states from that of the free benzene molecule, the benzene-benzene interaction has a more significant effect on the electronic states of benzene. VUV spectra of benzene and water layers show evidence of non-wetting between benzene and water, characterised by Rayleigh scattering tails at wavelengths greater than 220 nm. Our results also show evidence of benzene-water interaction at the benzene-water interface affecting both the benzene and the water electronic states. Annealing the mixtures and layers of benzene and water show that benzene remains trapped in/under water ice until water desorption near 160 K. These first systematic studies of binary amorphous mixtures in the VUV, supported with complementary IR studies, provide a deeper insight into the influence of intermolecular interactions on intramolecular electronic states with significant implications for our understanding of photochemical processes in more realistic astrochemical environments.
The method of laser-induced reaction (LIR) is used to obtain high-resolution IR spectra of CH2D(+) in collision with n-H2 at a nominal temperature of 14 K. For this purpose, a home-built optical parametric oscillator (OPO), tunable in the range of 2500-4000 cm(-1), has been coupled to a 22-pole ion trap apparatus. In total, 112 lines of the ν1 and ν4 bands have been recorded. A line list is inferred from a careful analysis of the shape of the LIR signal. Line positions have been determined to an accuracy of 1 × 10(-4) cm(-1), allowing for the prediction of pure rotational transitions with MHz accuracy. In addition, an IR-THz double-resonance LIR depletion technique is applied to H2D(+) to demonstrate the feasibility for pure rotational spectroscopy with LIR.
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