Guanglai Zhu

Molecular Insights into the Electric Double Layers of Ionic Liquids on Au(100) Electrodes

The electric double layer structure and differential capacitance of single crystalline Au(100) electrodes in the ionic liquid 1-butyl-3-methyl-imidazolium hexafluorophosphate are investigated using molecular dynamics simulations. Results show strong adsorption on the electrode surface. The potential of zero charge (pzc) and maxima of differential capacitance are strongly dependent on the adsorption layer structure. At potentials near the pzc, cations and anions adjacent to the electrode surface are coadsorbed on the same screening layer. This strong adsorption layer results in overscreening effects on the compact layer and induces both a bell-shaped differential capacitance curve and a positive pzc. Moreover, the potential required for transition from overscreening to overcrowding is about 4.0 V. This transition potential may be attributed to the higher interaction energy between the Au(100) electrode and ions compared with the binding energy in our cation-anion system.

Dilute or Concentrated Electrolyte Solutions? Insight from Ionic Liquid/Water Electrolytes

When room-temperature ionic liquids (IL) are used as an electrolyte, their transport behaviors are still under heavy debate due to their complicated ion-associations. In this article, we conducted molecular dynamics simulations to study the molecular scale ion associations from the very dilute 1-butyl-3-methylimidazolium iodide/water solution to the pure IL. It revealed that ions are localized in a multicoordinated ion cage structure with nanoseconds in concentrated IL solutions. Dynamics analyses indicate that the transport of this solution can be depicted by the Debye-Hückel model only in dilute IL/water electrolyte. The velocity and rotational correlation functions showed that the lifetime of translational and rotational motions are at the level of picoseconds and nanoseconds, respectively, because of the ion cage effect. The lifetime of ion association demonstrated that the recombination of association ions was prevalent in IL solutions. It means that the dipolar or stable contact ion-pairs model may not be suitable for depicting the IL transport.

Photosynthetic performance of Lycoris radiata var. radiata to shade treatments

The effects of shade on the growth, leaf photosynthetic characteristics, and chlorophyll (Chl) fluorescence parameters of Lycoris radiata var. radiata were determined under differing irradiances (15, 65, and 100% of full irradiance) within pots. The HI plants exhibited a typical decline in net photosynthetic rate (PN) during midday, which was not observed in MI- and LI plants. This indicated a possible photoinhibition in HI plants as the ratio of variable to maximum fluorescence (Fv/Fm) value was higher and the minimal fluorescence (F0) was lower in the, and LI plants. Diurnal patterns of stomatal conductance (gs) and transpiration rate (E) were remarkably similar to those of PN at each shade treatments, and the intercellular CO2 concentration (Ci) had the opposite change trend. Under both shading conditions, the light saturation point, light compensation point and photon-saturated photosynthetic rate (Pmax) became lower than those under full sunlight, and it was the opposite for the apparent quantum yield (AQY). The higher the level of shade, the lower the integrated daytime carbon gain, stomatal and epidermis cell densities, specific leaf mass (SLM), bulb mass ratio (BMR), leaf thickness, and Chl a/b ratio. In contrast, contents of Chls per dry mass (DM), leaf area ratio (LAR), leaf mass ratio (LMR), leaf length, leaf area and total leaf area per plant increased under the same shade levels to promote photon absorption and to compensate for the lower radiant energy. Therefore, when the integrated daytime carbon gain, leaf area and total leaf area per plant, which are the main factors determining the productivity of L. radiata var. radiata plant, were taken into account together, this species may be cultivated at about 60∼70% of ambient irradiance to promote its growth.

Effects of Ionic Liquid [bmim][PF6] on Absorption Spectra and Reaction Kinetics of the Duroquinone Triplet State in Acetonitrile

The transient absorption spectra and photoinduced electron-transfer process of duroquinone (DQ) in mixed binary solutions of ionic liquid (IL) [bmim][PF6] and acetonitrile (MeCN) have been investigated by laser photolysis at an excitation wavelength of 355 nm. A spectral blue shift of 3DQ* was observed in the IL/MeCN mixtures compared to MeCN. At lower VIL(volume fraction of IL), the interaction between DQ and the solvent is dominant, and the decay rate constant (kobs) of 3DQ* increases steadily with the increasing of VIL; to the contrary, at higher VIL, the network structures due to the hydrogen bond and viscosity are dominant, and the decay rate constant decreases obviously with increasing VIL. A critical point (turnover) was observed at VIL = approximately 0.30. The dependence of the observed growth rate (kgr) of the photoinduced electron-transfer (PET) products on VIL is complex and shows a special change; kgr first decreases with increasing VIL, then increases, and finally decreases slowly with further increasing of VIL. It is speculated that the PET process in the mixture can be affected by factors including the local structure and the reorganization energy of the solvent and salt and cage effects. The change of local structure of [bmim][PF6]/MeCN is supported by following the steady-state fluorescence behavior of the mixture, in combination with the molecular dynamics simulation of the thermodynamic property. The results revealed that the degree of self-aggregation of monomeric cations (bmim+) to associated forms increases with increasing VIL. This is in good agreement with the laser photolysis results for the same solutions.

Photoinduced electron transfer between 2-methylanthraquinone and triethylamine in an ionic liquid: Time-resolved EPR and transient absorption spectroscopy study

Photoinduced electron transfer between 2-methylanthraquinone (MeAQ) and triethylamine (TEA) in a room-temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF6]), was investigated by comparing the time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy and the transient absorption spectroscopy. The results of TR-EPR spectroscopy, in which MeAQ was 8 mmol L(-1) and TEA was 150 mmol L(-1), indicated that the transient radical would exist longer time in [bmim][PF6] than in acetonitrile. At the delay time of 8 μs after laser excitation, the TR-EPR signal transformed from an emissive peak into an absorptive peak when the experiment was performed in [bmim][PF6]. The results of the transient absorption spectroscopy, in which MeAQ was 0.1 mmol L(-1) and TEA was 2.2 mmol L(-1), showed that the efficiency and the rate of the photoinduced electron transfer reaction in [bmim][PF6] were obviously lower than that in acetonitrile. It was concluded that various factors, such as concentration, viscosity and local structural transformation of the solution, have an influence on the process of photoinduced electron transfer in [bmim][PF6].

Origin of heterogeneous dynamics in local molecular structures of ionic liquids

Room-temperature ionic liquids (ILs) are generally considered as structurally heterogeneous with inherent polar/apolar phase separation. However, even after a decade of research, local dynamics in the heterogeneous structures of ILs remain neglected. Such local dynamics may influence the ion transport of electrolytes, as well as the reaction rate of solvents. In this study, we performed molecular dynamics simulation to analyze the local dynamics for the structural heterogeneity of ILs. Calculations of the diffusion, reorientation, and association dynamics showed a distinct heterogeneous dynamics between the polar and apolar regions of ILs. Further studies demonstrated that such local dynamic differences originate from local structural heterogeneity. Different energy barriers determine a predominant fast reorientation dynamics in apolar regions and a locally vibrating behavior in polar regions. Additionally, we suggested a new jumping mechanism to clarify the dynamic heterogeneity of ions in the polar regions. The results will help determine the origin of the heterogeneous dynamics in IL local structures and provide a theoretical basis for tuning the dynamic properties of ILs used as electrolytes or reaction solvents.

Molecular insight into the microstructure and microscopic dynamics of pyridinium ionic liquids with different alkyl chains based on temperature response

The temperature dependence of the microstructure and microscopic dynamics of three N-alkylpyridinium tetrafluoroborate ionic liquids, namely, [BPy][BF4], [HPy][BF4], and [OPy][BF4], is investigated via molecular dynamics simulation. Under a temperature change, the microstructure changes of [OPy][BF4] with a longer alkyl chain show a slight difference from that of [BPy][BF4] and [HPy][BF4] in terms of the radial and spatial distribution functions. A temperature increase is found to be advantageous to the aggregation of the polar regions as well as the nonpolar regions in the pyridinium ionic liquids. However, the properties of the microscopic dynamics of the three ionic liquids regularly change under conditions with temperature change. The results show a decreased probability of ions to reverse the direction of their translation motion because the negative parts of the velocity autocorrelation functions increase with the temperature. The temperature dependence of rotational dynamics is more obvious than that of translation. A rise in temperature causes rotational autocorrelation functions to decay quickly, and it considerably reduces relaxation time. With an increase in alkyl chain length, the rotational correlation improves and the relaxation time decreases. The time correlation functions show that the association dynamics of nonpolar regions is faster than that of polar regions over time. The association time is short for long-tailed ionic liquids.

Time-Resolved Electron Paramagnetic Resonance Investigation on the Quenching Reaction of Photo-Induced Excited Triplet Vitamin K3 by Antioxidant Vitamin C in Homogeneous and Micelle Solutions

The reaction mechanism and dynamics of the quenching of the excited triplet of vitamin by vitamin C was studied in both homogenous ethylene glycol-H2O plus hexadecyltrimethylammonium bromide, aerosol OT, sodium dodecyl sulfate, and Triton X-100 micelle solutions by time-resolved electronic paramagnetic resonance. The photolysis of vitamin K3 in EG-H2O solution led to the chemically induced dynamic electron polarization (CIDEP) of the vitamin K3 neutral radical VK3H• and ethylene glycol ketyl radical, which showed that a hydrogen atom abstraction reaction of with the solvent ethylene glycol occurred. The triplet mechanism was the primary mechanism underlying the generation of CIDEP, suggesting that quickly reacted with ethylene glycol before spin-lattice relaxation. During the photolysis of vitamin K3 and vitamin C in ethylene glycol-H2O solution, abstracted hydrogen atoms not only from the solvent ethylene glycol but also from a vitamin C monoanion. The stronger CIDEP signal of the vitamin C monoanion radical indicated that can be rapidly quenched by vitamin C. In hexadecyltrimethylammonium bromide (aerosol OT, sodium dodecyl sulfate)/ethylene glycol-H2O micelle solutions, lipid-soluble needed to diffuse around the micelle surface to react with the water-soluble vitamin C. The spin-lattice relaxation of the parent resulted in weaker CIDEP of the reaction-generated radicals. Furthermore, the attraction between the positive charge layer of the hexadecyltrimethylammonium bromide micelle and vitamin C monoanion made the quenching reaction of by vitamin C rapid, whereas the repulsion between the negative charge layer of aerosol OT (sodium dodecyl sulfate) micelle and vitamin C monoanion made the quenching reaction slow. For Triton X-100 micelle, the coexistence of vitamin K3 and vitamin C in the same polyethylene glycol shell resulted in the fastest quenching reaction and strong CIDEP of the monoanion radical.