Lithium Ion Coupled Electron-Transfer Rates in Superconcentrated Electrolytes: Exploring the Bottlenecks for Fast Charge-Transfer Rates with LiMn2O4 Cathode Materials.

The charge-transfer kinetics of lithium ion intercalation into LixMn2O4 cathode materials was examined in dilute and concentrated aqueous and carbonate LiTFSI solutions using electrochemical methods. Distinctive trends in ion intercalation rates were observed between water-based and ethylene carbonate/diethyl carbonate solutions. The influence of the solution concentration on the rate of lithium ion transfer in aqueous media can be tentatively attributed to the process associated with Mn dissolution, whereas in carbonate solutions the rate is influenced by the formation of a concentration-dependent solid electrolyte interface (SEI). Some indications of SEI layer formation at electrode surfaces in carbonate solutions after cycling are detected by X-ray photoelectron spectroscopy. The general consequences related to the application of superconcentrated electrolytes for use in advanced energy storage cathodes are outlined and discussed.

A spectroscopic and computational study of Al(III) complexes in cryolite melts: Effect of cation nature.

Lithium, sodium and potassium cryolite melts are probed by Raman spectroscopy in a wide range of the melt composition. The experimental data demonstrate a slight red shift of main peaks and a decrease of their half-widths in the row Li(+), Na(+), K(+). Quantum chemical modelling of the systems is performed at the density functional theory level. The ionic environment is found to play a crucial role in the energy of fluoroaluminates. Potential energy surfaces describing the formation/dissociation of certain complex species, as well as model Raman spectra are constructed and compared with those obtained recently for sodium containing cryolite melts (R.R. Nazmutdinov, et al., Spectrochim, Acta A 75 (2010) 1244.). The calculations show that the cation nature affects the geometry of the ionic associates as well as the equilibrium and kinetics of the complexation processes. This enables to interpret both original experimental data and those reported in literature.

Exploring the energetics of water permeation in photosystem II by multiple steered molecular dynamics simulations.

The Mn(4)Ca cluster of the oxygen-evolving complex (OEC) of photosynthesis catalyzes the light-driven splitting of water into molecular oxygen, protons, and electrons. The OEC is buried within photosystem II (PSII), a multisubunit integral membrane protein complex, and water must find its way to the Mn(4)Ca cluster by moving through protein. Molecular dynamics simulations were used to determine the energetic barriers for water permeation though PSII extrinsic proteins. Potentials of mean force (PMFs) for water were derived by using the technique of multiple steered molecular dynamics (MSMD). Calculation of free energy profiles for water permeation allowed us to characterize previously identified water channels, and discover new pathways for water movement toward the Mn(4)Ca cluster. Our results identify the main constriction sites in these pathways which may serve as selectivity filters that restrict both the access of solutes detrimental to the water oxidation reaction and loss of Ca(2+) and Cl(-) from the active site.

A spectroscopic and computational study of Al(III) complexes in sodium cryolite melts: ionic composition in a wide range of cryolite ratios.

The structure of sodium cryolite melts was studied using Raman spectroscopy and quantum chemical calculations performed at the density functional theory level. The existence of bridged forms in the melts was argued first from the analysis of experimental Raman spectra. In the quantum chemical modelling emphasis was put on the construction of potential energy surfaces describing the formation/dissociation of certain complex species. Effects of the ionic environment were found to play a crucial role in the energetics of model processes. The structure of the simplest possible polymeric forms involving two Al centres linked through F atoms ("dimers") was thoroughly investigated. The calculated equilibrium constants and model Raman spectra yield additional evidence in favour of the dimers. This agrees with a self-consistent analysis of a series of Raman spectra for a wide range of the melt composition.

Pulsed and cw laser oscillations in LiF:F-2 color center crystal under laser diode pumping.

Continuous-wave laser oscillations in LiF:F-2 crystal optically pumped by a laser diode at 970 nm were demonstrated for what is believed to be the first time. The slope efficiency of 14% and conversion efficiency of 5.5% were achieved for 80 micros pump pulse duration and 5 Hz pulse repetition rate. An efficiency twice as low was measured at a 6.25 kHz pulse repetition rate (50% off-duty factor) and in cw mode of laser operation.

Laser and self-Raman-laser oscillations of PBMoO4:Nd3+ crystal under laser diode pumping.

Different regimes of laser operation and stimulated Raman scattering (SRS) for a laser diode (LD)-pumped PbMoO4:Nd3+ crystal have been investigated. Under 1.5 W LD pumping, the output power of the PbMoO4:Nd3+ laser in the free-running mode at 1056 nm reached 0.65 W with a slope efficiency of up to 53%. Using different LiF: F-2 saturable absorbers, we achieved a maximum pulse energy of 11 microJ at a 1.4 ns pulse duration and a maximum output power of 0.35 W (10 microJ) at a 7 ns pulse width in the passively Q-switched mode. PbMoO4:Nd3+ self-Raman-laser operation at 1163 nm (first Stokes) was obtained for the first time, to our knowledge. The self-Raman-laser output pulse energy was measured to be as high as 6 microJ and the pulse duration was estimated to be shorter than 500 ps.