A brief account of recent simulation and theoretical model studies of various solution-phase processes in room-temperature ionic liquids is given. These include structure and dynamics of equilibrium and nonequilibrium solvation, solute rotation and vibrational energy relaxation, and free energetics and dynamics of unimolecular electron-transfer reactions. Special attention is paid to both the aspects shared by and the contrasts with polar solvents under normal conditions. A brief comparison with available experiments is also made.

Dynamics of a coarse-grained model for the room-temperature ionic liquid, 1-ethyl-3-methylimidazolium hexafluorophosphate, couched in the united-atom site representation are studied via molecular dynamics simulations. The dynamically heterogeneous behavior of the model resembles that of fragile supercooled liquids. At or close to room temperature, the model ionic liquid exhibits slow dynamics, characterized by nonexponential structural relaxation and subdiffusive behavior. The structural relaxation time, closely related to the viscosity, shows a super-Arrhenius behavior. Local excitations, defined as the displacement of an ion exceeding a threshold distance, are found to be mainly responsible for structural relaxation in the alternating structure of cations and anions. As the temperature is lowered, excitations become progressively more correlated. This results in the decoupling of exchange and persistence times, reflecting a violation of the Stokes-Einstein relation.

Computationally predicting reverse intersystem crossing (RISC) rates is important for designing new thermally activated delayed fluorescence (TADF) materials. We report a method that can quantitatively predict RISC rates by explicitly considering the spin–vibronic coupling mechanism. The coupling element of the spin–vibronic Hamiltonian is obtained by expanding the spin–orbit and the non-Born–Oppenheimer terms to second order and is then brought into the Golden Rule rate under the Condon approximation. The rate equation is solved directly in the time domain using a correlation function approach. The contributions of the first-order direct spin–orbit coupling and the second-order spin–vibronic coupling to an RISC rate can be quantitatively analyzed in a separate manner. We demonstrate the utility of the method by applying it to a representative TADF system, where we observe that the spin–vibronic portion is substantial but not dominant especially with a relatively small triplet–singlet energy gap. Likewise, our method may elucidate the physical background of efficient nonradiative transitions from the lowest triplet to a higher lying singlet in other purely organic TADF systems, and it will be of great utility toward designing new such molecules.

Reorientational time correlation functions C(l)(t)( identical withP(l)[cos theta(t)]) for a diatomic solute in 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI(+)PF(6) (-)) are analyzed via molecular dynamics computer simulations, where <...> denotes an equilibrium ensemble average, P(l) the lth order Legendre polynomial and theta(t) the angle between the solute orientation at time t and its initial direction. Overall results are indicative of heterogeneous dynamics in EMI(+)PF(6) (-). For a small nondipolar solute, C(l)(t) are well-described as stretched exponential functions in wide time ranges. One striking feature is that after rapid initial relaxation, C(2)(t) decays more slowly than C(1)(t). As a result, the correlation time associated with the former is considerably longer than that with the latter. This is ascribed to solvent structural fluctuations, which allow large-amplitude solute rotations. As the solute size grows, relaxation of C(l)(t) approaches exponential decay.

Abstract. Iron dissolution from mineral dusts and soil particles is vital as a source of bioavailable iron in various environmental media. In this work, the dissolution of iron oxide particles trapped in ice was investigated as a new pathway of iron supply. The dissolution experiments were carried out in the absence and presence of various organic complexing ligands under dark condition. In acidic pH conditions (pH 2, 3, and 4), the dissolution of iron oxides was greatly enhanced in the ice phase compared to that in water. The dissolved iron was mainly in the ferric form, which indicates that the dissolution is not a reductive process. The extent of dissolved iron was greatly affected by the kind of organic complexing ligands and the surface area of iron oxides. The iron dissolution was most pronounced with high surface area iron oxides and in the presence of strong iron binding ligands. The enhanced dissolution of iron oxides in ice is mainly ascribed to the "freeze concentration effect", which concentrates iron oxide particles, organic ligands, and protons in the liquid like ice grain boundary region and accelerates the dissolution of iron oxides. The ice-enhanced dissolution effect gradually decreased when decreasing the freezing temperature from −10 to −196 • C, which implies that the presence and formation of the liquid-like ice grain boundary region play a critical role. The proposed phenomenon of enhanced dissolution of iron oxides in ice may provide a new pathway of bioavailable iron production. The frozen atmospheric ice with iron-containing dust particles in the upper atmosphere thaws upon descending and may provide bioavailable iron upon deposition onto the ocean surface.

The effects of solute polarizability on solvation and solute transport in the room-temperature ionic liquid 1-ethyl-3-methylimidazolium hexafluorophosphate (EMI+PF(6)-) are investigated via molecular dynamics simulations. A valence-bond description is employed to account for the instantaneous adjustment of the solute electronic charge distribution to the fluctuating solvent environment. It is found that the ultrafast inertial component of solvation dynamics becomes slower as the solute polarizability grows. Moreover, its contribution to overall solvent relaxation becomes reduced with increasing polarizability, especially in the case of nonequilibrium solvation dynamics. Overall, the inclusion of the solute electronic polarizability in the simulations improves the agreement with time-dependent Stokes shift measurements.

Although the organic light‐emitting diode (OLED) has been successfully commercialized, the development of deep‐blue OLEDs with high efficiency and long lifetime remains a challenge. Here, a novel hyperfluorescent OLED that incorporates the Pt(II) complex (PtON7‐dtb) as a phosphorescent sensitizer and a hydrocarbon‐based and multiple resonance‐based fluorophore as an emitter (TBPDP and ν‐DABNA) in the device emissive layer (EML), is proposed. Such an EML system can promote efficient energy transfer from the triplet excited states of the sensitizer to the singlet excited states of the fluorophore, thus significantly improving the efficiency and lifetime of the device. As a result, a deep‐blue hyperfluorescent OLED using a multiple resonance‐based fluorophore (ν‐DABNA) with Commission Internationale de L'Eclairage chromaticity coordinate y below 0.1 is demonstrated, which attains a narrow full width at half maximum of ≈17 nm, fourfold increased maximum current efficiency of 48.9 cd A−1, and 19‐fold improved half‐lifetime of 253.8 h at 1000 cd m−2 compared to a conventional phosphorescent OLED. The findings can lead to better understanding of the hyperfluorescent OLEDs with high performance.

Dissolution of iron from mineral dust particles greatly depends upon the type and amount of copresent inorganic anions. In this study, we investigated the roles of sulfate, chloride, nitrate, and perchlorate on the dissolution of maghemite and lepidocrocite in ice under both dark and UV irradiation and compared the results with those of their aqueous counterparts. After 96 h of reaction, the total dissolved iron in ice (pH 3 before freezing) was higher than that in the aqueous phase (pH 3) by 6-28 times and 10-20 times under dark and UV irradiation, respectively. Sulfuric acid was the most efficient in producing labile iron under dark condition, whereas hydrochloric acid induced the most dissolution of the total and ferrous iron in the presence of light. This ice-induced dissolution result was also confirmed with Arizona Test Dust (AZTD). In the freeze-thaw cycling test, the iron oxide samples containing chloride, nitrate, or perchlorate showed a similar extent of total dissolved iron after each cycling while the sulfate-containing sample rapidly lost its dissolution activity with repeating the cycle. This unique phenomenon observed in ice might be related to the freeze concentration of protons, iron oxides, and inorganic anions in the liquid-like ice grain boundary region. These results suggest that the ice-enhanced dissolution of iron oxides can be a potential source of bioavailable iron, and the acid anions critically influence this process.