Lattice Models of Ionic Systems

A theoretical analysis of Coulomb systems on lattices in general dimensions is presented. The thermodynamics is developed using Debye-Huckel theory with ion-pairing and dipole-ion solvation, specific calculations being performed for 3D lattices. As for continuum electrolytes, low-density results for sc, bcc and fcc lattices indicate the existence of gas-liquid phase separation. The predicted critical densities have values comparable to those of continuum ionic systems, while the critical temperatures are 60-70% higher. However, when the possibility of sublattice ordering as well as Debye screening is taken into account systematically, order-disorder transitions and a tricritical point are found on sc and bcc lattices, and gas-liquid coexistence is suppressed. Our results agree with recent Monte Carlo simulations of lattice electrolytes.Comment: 25 pages, 3 figures, ReVTeX 4, Submitted to J. Chem. Phy

Lattice Models of Ionic Systems with Charge Asymmetry

The thermodynamics of a charge-asymmetric lattice gas of positive ions carrying charge $q$ and negative ions with charge $-zq$ is investigated using Debye-H\"uckel theory. Explicit analytic and numerical calculations, which take into account the formation of neutral and charged clusters and cluster solvation by the residual ions, are performed for $z=2$, 3 and 4. As charge asymmetry increases, the predicted critical point shifts to lower temperatures and higher densities. This trend agrees well with the results from recent Monte Carlo simulations for continuum charge-asymmetric hard-sphere ionic fluids and with the corresponding predictions from continuum Debye-H\"uckel theory.Comment: submitted to J.Chem.Phy

Fermi-liquid theory of the surface impedance of a metal in a normal magnetic field

In this paper we present detailed theoretical analysis of the frequency and/or magnetic field dependence of the surface impedance of a metal at the anomalous skin effect. We calculate the surface impedance in the presence of a magnetic field directed along the normal to the metal surface. The effects of the Fermi-liquid interactions on the surface impedance are studied. It is shown that the cyclotron resonance in a normal magnetic field may be revealed {\it only and exclusively} in such metals whose Fermi surfaces include segments where its Gaussian curvature turns zero. The results could be applied to extract extra informations concerning local anomalies in the Fermi surface curvature in conventional and quasi-two-dimensional metals.Comment: 10 pages, 1 figure, text added and rearranged, computational details are moved into Appendice

Effect of the entropy on the shear viscosity of metallic glasses near the glass transition

We measured the shear viscosity of 14 metallic glasses differing with their mixing entropy $\Delta S_{mix}$. It is found that the viscosity at the glass transition temperature $T_g$ significantly increases with $\Delta S_{mix}$. Using calorimetric data, we calculated the excess entropy of all glasses $\Delta S$ with respect to their maternal crystalline states as a function of temperature. It is shown that the excess entropy $\Delta S$ both at room temperature and at $T_g$ \textit{decreases} with $\Delta S_{mix}$. It is concluded that glasses with "high mixing entropy" $\Delta S_{mix}$ correspond to MGs with \textit{low} excess entropy $\Delta S$. The origin of the increased shear viscosity at $T_g$ of glasses with high $\Delta S_{mix}$ is determined by their reduced excess entropy $\Delta S$.Comment: 12 pages, 4 Figure

Relation of the thermodynamic parameter of disordering with the width of structure factor and defect concentration in a metallic glass

In this work, we show that above the glass transition there exists a strong unique interrelationship between the thermodynamic parameter of disorder of a metallic glass derived using its excess entropy, diffraction measure of disorder given by the width of the X-ray structure factor and defect concentration derived from shear modulus measurements. Below the glass transition, this relationship is more complicated and depends on both temperature and thermal prehistory.Comment: 6 pages, 2 Figure

Thermodynamics of Electrolytes on Anisotropic Lattices

The phase behavior of ionic fluids on simple cubic and tetragonal (anisotropic) lattices has been studied by grand canonical Monte Carlo simulations. Systems with both the true lattice Coulombic potential and continuous-space $1/r$ electrostatic interactions have been investigated. At all degrees of anisotropy, only coexistence between a disordered low-density phase and an ordered high-density phase with the structure similar to ionic crystal was found, in contrast to recent theoretical predictions. Tricritical parameters were determined to be monotonously increasing functions of anisotropy parameters which is consistent with theoretical calculations based on the Debye-H\"uckel approach. At large anisotropies a two-dimensional-like behavior is observed, from which we estimated the dimensionless tricritical temperature and density for the two-dimensional square lattice electrolyte to be $T^*_{tri}=0.14$ and $\rho^*_{tri} = 0.70$.Comment: submitted to PR

Critical behavior of the fluctuation heat capacity near the glass transition of metallic glasses

The high-frequency shear modulus of five Zr-, Pd-, Cu-based conventional and two high-entropy bulk metallic glasses was measured in a wide temperature range up to the beginning of crystallization. Using these data and general thermodynamic relations, the "fluctuation" heat capacity $\Delta C_f$ determined by local structural fluctuations in the defect regions is introduced and calculated. It is found that $\Delta C_f$ temperature dependence for all metallic glasses has a large peak located slightly below or above the glass transition temperature but clearly lower than the crystallization onset temperature. The form of this peak resembles the characteristic $\lambda$-peak typical for order-disorder phase transitions. It is suggested that this $\Delta C_f$-peak reflects certain underlying critical phenomenon. The critical temperature $T_0$ (peak temperature) and corresponding critical index $\alpha$ are determined. Averaged over all seven metallic glasses under investigation in the initial and relaxed states, the critical index $\alpha=0.26$. The results obtained indicate that the fluctuations of thermal energy near the glass transition bear the marks of a continuous phase transition. However, the derived critical index is between those corresponding to a second-order phase transition ($\alpha\approx 0.1$) and a critical transition characterized by a tricritical point ($\alpha \approx 0.5$).Comment: 18 pages, 4 figure

Origin of elemental carbon in snow from western Siberia and northwestern European Russia during winter-spring 2014, 2015 and 2016

Short-lived climate forcers have been proven important both for the climate and human health. In particular, black carbon (BC) is an important climate forcer both as an aerosol and when deposited on snow and ice surface because of its strong light absorption. This paper presents measurements of elemental carbon (EC; a measurement-based definition of BC) in snow collected from western Siberia and northwestern European Russia during 2014, 2015 and 2016. The Russian Arctic is of great interest to the scientific community due to the large uncertainty of emission sources there. We have determined the major contributing sources of BC in snow in western Siberia and northwestern European Russia using a Lagrangian atmospheric transport model. For the first time, we use a recently developed feature that calculates deposition in backward (so-called retroplume) simulations allowing estimation of the specific locations of sources that contribute to the deposited mass

Intermolecular Photocatalytic Chemo‐, Stereo‐ and Regioselective Thiol–Yne–Ene Coupling Reaction

The first example of an intermolecular thiol–yne–ene coupling reaction is reported for the one-pot construction of C−S and C−C bonds. Thiol–yne–ene coupling opens a new dimension in building molecular complexity to access densely functionalized products. The employment of Eosin Y/DBU/MeOH photocatalytic system suppresses hydrogen atom transfer (HAT) and associative reductant upconversion (via C−S three-electron σ-bond formation). Investigation of the reaction mechanism by combining online ESI-UHRMS, EPR spectroscopy, isotope labeling, determination of quantum yield, cyclic voltammetry, Stern–Volmer measurements and computational modeling revealed a unique photoredox cycle with four radical-involving stages. As a result, previously unavailable products of the thiol–yne–ene reaction were obtained in good yields with high selectivity. They can serve as stable precursors for synthesizing synthetically demanding activated 1,3-dienes

Origin of elemental carbon in snow from western Siberia and northwestern European Russia during winter–spring 2014, 2015 and 2016

Short-lived climate forcers have been proven important both for the climate and human health. In particular, black carbon (BC) is an important climate forcer both as an aerosol and when deposited on snow and ice surface because of its strong light absorption. This paper presents measurements of elemental carbon (EC; a measurement-based definition of BC) in snow collected from western Siberia and northwestern European Russia during 2014, 2015 and 2016. The Russian Arctic is of great interest to the scientific community due to the large uncertainty of emission sources there. We have determined the major contributing sources of BC in snow in western Siberia and northwestern European Russia using a Lagrangian atmospheric transport model. For the first time, we use a recently developed feature that calculates deposition in backward (so-called retroplume) simulations allowing estimation of the specific locations of sources that contribute to the deposited mass. EC concentrations in snow from western Siberia and northwestern European Russia were highly variable depending on the sampling location. Modelled BC and measured EC were moderately correlated (R = 0.53–0.83) and a systematic region-specific model underestimation was found. The model underestimated observations by 42 % (RMSE  =  49 ng g−1) in 2014, 48 % (RMSE  =  37 ng g−1) in 2015 and 27 % (RMSE  =  43 ng g−1) in 2016. For EC sampled in northwestern European Russia the underestimation by the model was smaller (fractional bias, FB  >  −100 %). In this region, the major sources were transportation activities and domestic combustion in Finland. When sampling shifted to western Siberia, the model underestimation was more significant (FB  <  −100 %). There, the sources included emissions from gas flaring as a major contributor to snow BC. The accuracy of the model calculations was also evaluated using two independent datasets of BC measurements in snow covering the entire Arctic. The model underestimated BC concentrations in snow especially for samples collected in springtime