X-ray scattering and molecular dynamics simulations have been carried out to investigate structural differences and similarities in the condensed phase between pyrrolidinium-based ionic liquids paired with the bis(trifluoromethylsulfonyl)amide (NTf2(-)) anion where the cationic tail is linear, branched, or cyclic. This is important in light of the charge and polarity type alternations that have recently been shown to be present in the case of liquids with cations of moderately long linear tails. For this study, we have chosen to use the 1-alkyl-1-methylpyrrolidinium, Pyrr(1,n(+)) with n = 5 or 7, as systems with linear tails, 1-(2-ethylhexyl)-1-methylpyrrolidinium, Pyrr(1,EtHx(+)), as a system with a branched tail, and 1-(cyclohexylmethyl)-1-methylpyrrolidinium, Pyrr(1,ChxMe(+)), as a system with a cyclic tail. We put these results into context by comparing these data with recently published results for the Pyrr(1,n(+))/NTf2(-) ionic liquids with n = 4, 6, 8, and 10.1,2 General methods for interpreting the structure function S(q) in terms of q-dependent natural partitionings are described. This allows for an in-depth analysis of the scattering data based on molecular dynamics (MD) trajectories that highlight the effect of modifying the cationic tail.

On time scales of a nanosecond or less, radiolytically-generated excess electrons in ionic liquids undergo solvation processes and reactions that determine all subsequent chemistry and the accumulation of radiolytic damage. Using picosecond pulse radiolysis detection methods, we observed and quantified the solvation response of the electron in 1-methyl-1-butyl-pyrrolidinium bis (trifluoromethylsulfonyl)amide and used it to understand electron scavenging by a typical solute, duroquinone.

By monitoring coherent transition radiation (CTR) with a Michelson interferometer, bunch length measurement was investigated. Less-than-20-fs electron bunches were generated by a photocathode-based linear accelerator (linac) and a magnetic bunch compressor. From the femtosecond electron bunch of 2.1 pC and 32 MeV, CTR was measured using a Michelson interferometer that had two detectors with different spectral ranges, which enhanced the detection spectral range of CTR (ranging from 3 to 50 THz) and enabled us to determine the bunch length of the electron bunch. A model based on the interferometer's frequency sensitivity was proposed and introduced to analyze the measured interferograms. The measured interferograms and the frequency spectra were explained using the model.

Alcohol concentration dependences of photoinduced charge separation (CS) reaction of zinc tetraphenyl-porphyrin (ZnTPP) and duroquinone (DQ) were investigated in benzonitrile by a nanosecond laser flash photolysis technique. The photoinduced CS reaction was accelerated by the addition of alcohols, whereas the addition of acetonitrile caused little effect on the CS reactions. The simple theory was developed to calculate an increase in reorganization energies induced by the hydrogen bonding interactions between DQ and alcohols using the chemical equilibrium constants for the hydrogen bonding complexes through the concerted pathway and the stepwise one. The experimental results were analyzed by using the Marcus equation where we took into account the hydrogen bonding effects on the reorganization energy and the reaction free energy for the CS reaction. The observed alcohol concentration dependence of the CS reaction rates was well explained by the formation of the hydrogen bonding complexes through the concerted pathway, demonstrating the increase in the reorganization energy by the hydrogen bonding interactions.

Delayed fluorescence resulting from triplet–triplet annihilation in crystalline 9,10-diphenylanthracene was observed by means of steady-state fluorescence measurements under magnetic fields of ≤10 T. At five specific magnetic fields, four peaks and one dip in the magnetic field dependence of fluorescence intensity were observed, proving that exchange-coupled triplet pairs were generated in the course of triplet–triplet annihilation. The dip was in the opposite direction predicted for singlet channel triplet–triplet annihilation. Further analysis using the stochastic Liouville equation confirmed that the closest exchange-coupled triplet pair in crystalline 9,10-diphenylanthracene is quenched via both triplet channel and singlet channel triplet–triplet annihilation.