Assessment of the RE(OH)3 Ising magnetic materials as possible candidates for the study of transverse-field-induced quantum phase transitions

The LiHoxY1−xF4 Ising magnetic material subject to a magnetic field perpendicular to the Ho3+ Ising direction has shown over the past 20 years to be a host of very interesting thermodynamic and magnetic phenomena. Unfortunately, the availability of other magnetic materials other than LiHoxY1−xF4 that may be described by a transverse-field Ising model remains very much limited. It is in this context that we use here a mean-field theory to investigate the suitability of the Ho(OH)3, Dy(OH)3, and Tb(OH)3 insulating hexagonal dipolar Ising-type ferromagnets for the study of the quantum phase transition induced by a magnetic field, Bx, applied perpendicular to the Ising spin direction. Experimentally, the zero-field critical (Curie) temperatures are known to be Tc≈2.54, 3.48, and 3.72 K, for Ho(OH)3, Dy(OH)3, and Tb(OH)3, respectively. From our calculations we estimate the critical transverse field, Bxc, to destroy ferromagnetic order at zero temperature to be Bxc=4.35, 5.03, and 54.81 T for Ho(OH)3, Dy(OH)3, and Tb(OH)3, respectively. We find that Ho(OH)3, similarly to LiHoF4, can be quantitatively described by an effective S=1/2 transverse-field Ising model. This is not the case for Dy(OH)3 due to the strong admixing between the ground doublet and first excited doublet induced by the dipolar interactions. Furthermore, we find that the paramagnetic (PM) to ferromagnetic (FM) transition in Dy(OH)3 becomes first order for strong Bx and low temperatures. Hence, the PM to FM zero-temperature transition in Dy(OH)3 may be first order and not quantum critical. We investigate the effect of competing antiferromagnetic nearest-neighbor exchange and applied magnetic field, Bz, along the Ising spin direction ẑ on the first-order transition in Dy(OH)3. We conclude from these preliminary calculations that Ho(OH)3 and Dy(OH)3 and their Y3+ diamagnetically diluted variants, HoxY1−x(OH)3 and DyxY1−x(OH)3, are potentially interesting systems to study transverse-field-induced quantum fluctuations effects in hard axis (Ising-type) magnetic materials.

Induced random fields in the LiHoxY1-xF4 quantum ising magnet in a transverse magnetic field

The LiHoxY1-xF4 magnetic material in a transverse magnetic field Bxx̂ perpendicular to the Ising spin direction has long been used to study tunable quantum phase transitions in a random disordered system. We show that the Bx-induced magnetization along the x̂ direction, combined with the local random dilution-induced destruction of crystalline symmetries, generates, via the predominant dipolar interactions between Ho3+ ions, random fields along the Ising ẑ direction. This identifies LiHoxY1-xF4 in Bx as a new random field Ising system. The random fields explain the rapid decrease of the critical temperature in the diluted ferromagnetic regime and the smearing of the nonlinear susceptibility at the spin-glass transition with increasing Bx and render the Bx-induced quantum criticality in LiHoxY1-xF4 likely inaccessible.

π-dimerization of pleiadiene radical cations at low temperatures revealed by UV–vis spectroelectrochemistry and quantum theory

One-electron oxidation of the non-alternant polycyclic aromatic hydrocarbon pleiadiene and related cyclohepta[ c,d]pyrene and cyclohepta[c,d]fluoranthene in THF produces corresponding radical cations detectable in the temperature range of 293–263 K only on the subsecond time scale of cyclic voltammetry. Although the EPR-active red-coloured pleiadiene radical cation is stable according to the literature in concentrated sulfuric acid, spectroelectrochemical measurements reported in this study provide convincing evidence for its facile conversion into the green-coloured, formally closed shell and, hence, EPRsilent π-bound dimer dication stable in THF at 253 K. The unexpected formation of the thermally unstable dimeric product featuring a characteristic intense low-energy absorption band at 673 nm (1.84 eV; logεmax=4.0) is substantiated by ab initio calculations on the parent pleiadiene molecule and the PF6 − salts of the corresponding radical cation and dimer dication. The latter is stabilized with respect to the radical cation by 14.40 kcal mol−1 (DFT B3LYP) [37.64 kcal mol−1 (CASPT2/DFT B3LYP)]. An excellent match has been obtained between the experimental and TDDFT- calculated UV–vis spectra of the PF6 − salt of the pleiadiene dimer dication, considering solvent (THF) effects.

Molecular modelling studies of binding of DACD derivatives into G-Quadruplex DNA: comparison of force field and quantum polarized ligand docking methods

The DNA G-qadruplexes are one of the targets being actively explored for anti-cancer therapy by inhibiting them through small molecules. This computational study was conducted to predict the binding strengths and orientations of a set of novel dimethyl-amino-ethyl-acridine (DACA) analogues that are designed and synthesized in our laboratory, but did not diffract in Synchrotron light.Thecrystal structure of DNA G-Quadruplex(TGGGGT)4(PDB: 1O0K) was used as target for their binding properties in our studies.We used both the force field (FF) and QM/MM derived atomic charge schemes simultaneously for comparing the predictions of drug binding modes and their energetics. This study evaluates the comparative performance of fixed point charge based Glide XP docking and the quantum polarized ligand docking schemes. These results will provide insights on the effects of including or ignoring the drug-receptor interfacial polarization events in molecular docking simulations, which in turn, will aid the rational selection of computational methods at different levels of theory in future drug design programs. Plenty of molecular modelling tools and methods currently exist for modelling drug-receptor or protein-protein, or DNA-protein interactionssat different levels of complexities.Yet, the capasity of such tools to describevarious physico-chemical propertiesmore accuratelyis the next step ahead in currentresearch.Especially, the usage of most accurate methods in quantum mechanics(QM) is severely restricted by theirtedious nature. Though the usage of massively parallel super computing environments resulted in a tremendous improvement in molecular mechanics (MM) calculations like molecular dynamics,they are still capable of dealing with only a couple of tens to hundreds of atoms for QM methods. One such efficient strategy that utilizes thepowers of both MM and QM are the QM/MM hybrid methods. Lately, attempts have been directed towards the goal of deploying several different QM methods for betterment of force field based simulations, but with practical restrictions in place. One of such methods utilizes the inclusion of charge polarization events at the drug-receptor interface, that is not explicitly present in the MM FF.

On the quantum mechanical scattering statistics of many particles

The probability of a quantum particle being detected in a given solid angle is determined by the S-matrix. The explanation of this fact in time-dependent scattering theory is often linked to the quantum flux, since the quantum flux integrated against a (detector-) surface and over a time interval can be viewed as the probability that the particle crosses this surface within the given time interval. Regarding many particle scattering, however, this argument is no longer valid, as each particle arrives at the detector at its own random time. While various treatments of this problem can be envisaged, here we present a straightforward Bohmian analysis of many particle potential scattering from which the S-matrix probability emerges in the limit of large distances.

Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

Quantifying the contributions to stratospheric ozone changes from ozone depleting substances and greenhouse gases

A state-of-the-art chemistry climate model coupled to a three-dimensional ocean model is used to produce three experiments, all seamlessly covering the period 1950–2100, forced by different combinations of long-lived Greenhouse Gases (GHGs) and Ozone Depleting Substances (ODSs). The experiments are designed to quantify the separate effects of GHGs and ODSs on the evolution of ozone, as well as the extent to which these effects are independent of each other, by alternately holding one set of these two forcings constant in combination with a third experiment where both ODSs and GHGs vary. We estimate that up to the year 2000 the net decrease in the column amount of ozone above 20 hPa is approximately 75% of the decrease that can be attributed to ODSs due to the offsetting effects of cooling by increased CO2. Over the 21st century, as ODSs decrease, continued cooling from CO2 is projected to account for more than 50% of the projected increase in ozone above 20 hPa. Changes in ozone below 20 hPa show a redistribution of ozone from tropical to extra-tropical latitudes with an increase in the Brewer-Dobson circulation. In addition to a latitudinal redistribution of ozone, we find that the globally averaged column amount of ozone below 20 hPa decreases over the 21st century, which significantly mitigates the effect of upper stratospheric cooling on total column ozone. Analysis by linear regression shows that the recovery of ozone from the effects of ODSs generally follows the decline in reactive chlorine and bromine levels, with the exception of the lower polar stratosphere where recovery of ozone in the second half of the 21st century is slower than would be indicated by the decline in reactive chlorine and bromine concentrations. These results also reveal the degree to which GHGrelated effects mute the chemical effects of N2O on ozone in the standard future scenario used for the WMO Ozone Assessment. Increases in the residual circulation of the atmosphere and chemical effects from CO2 cooling more than halve the increase in reactive nitrogen in the mid to upper stratosphere that results from the specified increase in N2O between 1950 and 2100.

Seasonal persistence of northern low- and middle-latitude anomalies of ozone and other trace gases in the upper stratosphere

Analysis of observed ozone profiles in Northern Hemisphere low and middle latitudes reveals the seasonal persistence of ozone anomalies in both the lower and upper stratosphere. Principal component analysis is used to detect that above 16 hPa the persistence is strongest in the latitude band 15–45°N, while below 16 hPa the strongest persistence is found over 45–60°N. In both cases, ozone anomalies persist through the entire year from November to October. The persistence of ozone anomalies in the lower stratosphere is presumably related to the wintertime ozone buildup with subsequent photochemical relaxation through summer, as previously found for total ozone. The persistence in the upper stratosphere is more surprising, given the short lifetime of Ox at these altitudes. It is hypothesized that this “seasonal memory” in the upper stratospheric ozone anomalies arises from the seasonal persistence of transport-induced wintertime NOy anomalies, which then perturb the ozone chemistry throughout the rest of the year. This hypothesis is confirmed by analysis of observations of NO2, NOx, and various long-lived trace gases in the upper stratosphere, which are found to exhibit the same seasonal persistence. Previous studies have attributed much of the year-to-year variability in wintertime extratropical upper stratospheric ozone to the Quasi-Biennial Oscillation (QBO) through transport-induced NOy (and hence NO2) anomalies but have not identified any statistical connection between the QBO and summertime ozone variability. Our results imply that through this “seasonal memory,” the QBO has an asynchronous effect on ozone in the low to midlatitude upper stratosphere during summer and early autumn.

On the attribution of stratospheric ozone and temperature changes to changes in ozone-depleting substances and well-mixed greenhouse gases

The vertical profile of global-mean stratospheric temperature changes has traditionally represented an important diagnostic for the attribution of the cooling effects of stratospheric ozone depletion and CO2 increases. However, CO2-induced cooling alters ozone abundance by perturbing ozone chemistry, thereby coupling the stratospheric ozone and temperature responses to changes in CO2 and ozone-depleting substances (ODSs). Here we untangle the ozone-temperature coupling and show that the attribution of global-mean stratospheric temperature changes to CO2 and ODS changes (which are the true anthropogenic forcing agents) can be quite different from the traditional attribution to CO2 and ozone changes. The significance of these effects is quantified empirically using simulations from a three-dimensional chemistry-climate model. The results confirm the essential validity of the traditional approach in attributing changes during the past period of rapid ODS increases, although we find that about 10% of the upper stratospheric ozone decrease from ODS increases over the period 1975–1995 was offset by the increase in CO2, and the CO2-induced cooling in the upper stratosphere has been somewhat overestimated. When considering ozone recovery, however, the ozone-temperature coupling is a first-order effect; fully 2/5 of the upper stratospheric ozone increase projected to occur from 2010–2040 is attributable to CO2 increases. Thus, it has now become necessary to base attribution of global-mean stratospheric temperature changes on CO2 and ODS changes rather than on CO2 and ozone changes.

The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed.

Pervasive environment for gases detection and collapses in underground mines

Safety is an element of extreme priority in mining operations, currently many traditional mining countries are investing in the implementation of wireless sensors capable of detecting risk factors; through early warning signs to prevent accidents and significant economic losses. The objective of this research is to contribute to the implementation of sensors for continuous monitoring inside underground mines providing technical parameters for the design of sensor networks applied in underground coal mines. The application of sensors capable of measuring in real time variables of interest, promises to be of great impact on safety for mining industry. The relationship between the geological conditions and mining method design, establish how to implement a system of continuous monitoring. In this paper, the main causes of accidents for underground coal mines are established based on existing worldwide reports. Variables (temperature, gas, structural faults, fires) that can be related to the most frequent causes of disaster and its relevant measuring range are then presented, also the advantages, management and mining operations are discussed, including the analyzed of applying these systems in terms of Benefit, Opportunity, Cost and Risk. The publication focuses on coal mining, based on the proportion of these events a year worldwide, where a significant number of workers are seriously injured or killed. Finally, a dynamic assessment of safety at underground mines it is proposed, this approach offers a contribution to design personalized monitoring networks, the experience developed in coal mines provides a tool that facilitates the application development of technology within underground coal mines.

A parallel quantum histogram architecture

A parallel formulation of an algorithm for the histogram computation of n data items using an on-the-fly data decomposition and a novel quantum-like representation (QR) is developed. The QR transformation separates multiple data read operations from multiple bin update operations thereby making it easier to bind data items into their corresponding histogram bins. Under this model the steps required to compute the histogram is n/s + t steps, where s is a speedup factor and t is associated with pipeline latency. Here, we show that an overall speedup factor, s, is available for up to an eightfold acceleration. Our evaluation also shows that each one of these cells requires less area/time complexity compared to similar proposals found in the literature.