More Like this

1. Dataset of theoretical multinary perovskite oxides

   https://doi.org/10.1038/s41597-023-02127-w  

   Bare, Zachary J.; Morelock, Ryan J.; Musgrave, Charles B. (December 2023, Scientific Data)

   Abstract Perovskite oxides (ternary chemical formula ABO₃) are a diverse class of materials with applications including heterogeneous catalysis, solid-oxide fuel cells, thermochemical conversion, and oxygen transport membranes. However, their multicomponent (chemical formula$${A}_{x}{A}_{1-x}^{\text{'}}{B}_{y}{B}_{1-y}^{\text{'}}{O}_{3}$$ $A_x{A}_{1-x}^{\text{'}}{B}_y{B}_{1-y}^{\text{'}}{O}_3$) chemical space is underexplored due to the immense number of possible compositions. To expand the number of computed$${A}_{x}{A}_{1-x}^{{\prime} }{B}_{y}{B}_{1-y}^{{\prime} }{O}_{3}$$ $A_x{A}_{1-x}^{\prime }{B}_y{B}_{1-y}^{\prime }{O}_3$compounds we report a dataset of 66,516 theoretical multinary oxides, 59,708 of which are perovskites. First, 69,407$${A}_{0.5}{A}_{0.5}^{{\prime} }{B}_{0.5}{B}_{0.5}^{{\prime} }{O}_{3}$$ $A_{0.5}{A}_{0.5}^{\prime }{B}_{0.5}{B}_{0.5}^{\prime }{O}_3$compositions were generated in thea⁻b⁺a⁻Glazer tilting mode using the computationally-inexpensive Structure Prediction and Diagnostic Software (SPuDS) program. Next, we optimized these structures with density functional theory (DFT) using parameters compatible with the Materials Project (MP) database. Our dataset contains these optimized structures and their formation (ΔH_f) and decomposition enthalpies (ΔH_d) computed relative to MP tabulated elemental references and competing phases, respectively. This dataset can be mined, used to train machine learning models, and rapidly and systematically expanded by optimizing more SPuDS-generated$${A}_{0.5}{A}_{0.5}^{{\prime} }{B}_{0.5}{B}_{0.5}^{{\prime} }{O}_{3}$$ $A_{0.5}{A}_{0.5}^{\prime }{B}_{0.5}{B}_{0.5}^{\prime }{O}_3$perovskite structures using MP-compatible DFT calculations. 

   more » « less
2. Isoprene chemistry under upper-tropospheric conditions

   https://doi.org/10.1038/s41467-025-64229-w  

   Russell, Douglas M; Kunkler, Felix; Shen, Jiali; Kohl, Matthias; DeVivo, Jenna; Bhattacharyya, Nirvan; Xenofontos, Christos; Klebach, Hannah; Caudillo-Plath, Lucía; Simon, Mario; et al (December 2025, Nature Communications)

   Abstract Isoprene (C₅H₈) is the non-methane hydrocarbon with the highest emissions to the atmosphere. It is mainly produced by vegetation, especially broad-leaved trees, and efficiently transported to the upper troposphere in deep convective clouds, where it is mixed with lightning NO_x. Isoprene oxidation products drive rapid formation and growth of new particles in the tropical upper troposphere. However, isoprene oxidation pathways at low temperatures are not well understood. Here, in experiments at the CERN CLOUD chamber at 223 K and 243 K, we find that isoprene oxygenated organic molecules (IP-OOM) all involve two successive$${{{\rm{OH}}}}^{\bullet}$$ ${\mathrm{OH}}^{\bullet }$oxidations. However, depending on the ambient concentrations of the termination radicals ($${{{{\rm{HO}}}}_{2}}^{\bullet},\,{{{\rm{NO}}}}^{\bullet}$$ ${{\mathrm{HO}}_2}^{\bullet },{\mathrm{NO}}^{\bullet }$, and$${{{\rm{NO}}}}_{2}^{\bullet}$$ ${\mathrm{NO}}_2^{\bullet }$), vastly-different IP-OOM emerge, comprising compounds with zero, one or two nitrogen atoms. Our findings indicate high IP-OOM production rates for the tropical upper troposphere, mainly resulting in nitrate IP-OOM but with an increasing non-nitrate fraction around midday, in close agreement with aircraft observations. 

   more » « less
3. Evidence of a liquid–liquid phase transition in H$$_2$$O and D$$_2$$O from path-integral molecular dynamics simulations

   https://doi.org/10.1038/s41598-022-09525-x  

   Eltareb, Ali; Lopez, Gustavo E.; Giovambattista, Nicolas (April 2022, Scientific Reports)

   Abstract We perform path-integral molecular dynamics (PIMD), ring-polymer MD (RPMD), and classical MD simulations of H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O using the q-TIP4P/F water model over a wide range of temperatures and pressures. The density$$\rho (T)$$ $\rho \left(T\right)$, isothermal compressibility$$\kappa _T(T)$$ ${\kappa }_T\left(T\right)$, and self-diffusion coefficientsD(T) of H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O are in excellent agreement with available experimental data; the isobaric heat capacity$$C_P(T)$$ $C_P\left(T\right)$obtained from PIMD and MD simulations agree qualitatively well with the experiments. Some of these thermodynamic properties exhibit anomalous maxima upon isobaric cooling, consistent with recent experiments and with the possibility that H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O exhibit a liquid-liquid critical point (LLCP) at low temperatures and positive pressures. The data from PIMD/MD for H$$_2$$ ${}_2$O and D$$_2$$ ${}_2$O can be fitted remarkably well using the Two-State-Equation-of-State (TSEOS). Using the TSEOS, we estimate that the LLCP for q-TIP4P/F H$$_2$$ ${}_2$O, from PIMD simulations, is located at$$P_c = 167 \pm 9$$ $P_c=167\pm 9$ MPa,$$T_c = 159 \pm 6$$ $T_c=159\pm 6$ K, and$$\rho _c = 1.02 \pm 0.01$$ ${\rho }_c=1.02\pm 0.01$ g/cm$$^3$$ ${}^3$. Isotope substitution effects are important; the LLCP location in q-TIP4P/F D$$_2$$ ${}_2$O is estimated to be$$P_c = 176 \pm 4$$ $P_c=176\pm 4$ MPa,$$T_c = 177 \pm 2$$ $T_c=177\pm 2$ K, and$$\rho _c = 1.13 \pm 0.01$$ ${\rho }_c=1.13\pm 0.01$ g/cm$$^3$$ ${}^3$. Interestingly, for the water model studied, differences in the LLCP location from PIMD and MD simulations suggest that nuclear quantum effects (i.e., atoms delocalization) play an important role in the thermodynamics of water around the LLCP (from the MD simulations of q-TIP4P/F water,$$P_c = 203 \pm 4$$ $P_c=203\pm 4$ MPa,$$T_c = 175 \pm 2$$ $T_c=175\pm 2$ K, and$$\rho _c = 1.03 \pm 0.01$$ ${\rho }_c=1.03\pm 0.01$ g/cm$$^3$$ ${}^3$). Overall, our results strongly support the LLPT scenario to explain water anomalous behavior, independently of the fundamental differences between classical MD and PIMD techniques. The reported values of$$T_c$$ $T_c$for D$$_2$$ ${}_2$O and, particularly, H$$_2$$ ${}_2$O suggest that improved water models are needed for the study of supercooled water. 

   more » « less
4. On a Traveling Salesman Problem for Points in the Unit Cube

   https://doi.org/10.1007/s00453-024-01257-w  

   Balogh, József; Clemen, Felix Christian; Dumitrescu, Adrian (September 2024, Algorithmica)

   Abstract LetXbe ann-element point set in thek-dimensional unit cube$$[0,1]^k$$ ${[0,1]}^k$where$$k \ge 2$$ $k\ge 2$. According to an old result of Bollobás and Meir (Oper Res Lett 11:19–21, 1992) , there exists a cycle (tour)$$x_1, x_2, \ldots , x_n$$ $x_1,x_2,\dots ,x_n$through thenpoints, such that$$\left( \sum _{i=1}^n |x_i - x_{i+1}|^k \right) ^{1/k} \le c_k$$ ${\left({\sum }_{i=1}^n,{|x_i-x_{i+1}|}^k\right)}^{1/k}\le c_k$, where$$|x-y|$$ $|x-y|$is the Euclidean distance betweenxandy, and$$c_k$$ $c_k$is an absolute constant that depends only onk, where$$x_{n+1} \equiv x_1$$ $x_{n+1}\equiv x_1$. From the other direction, for every$$k \ge 2$$ $k\ge 2$and$$n \ge 2$$ $n\ge 2$, there existnpoints in$$[0,1]^k$$ ${[0,1]}^k$, such that their shortest tour satisfies$$\left( \sum _{i=1}^n |x_i - x_{i+1}|^k \right) ^{1/k} = 2^{1/k} \cdot \sqrt{k}$$ ${\left({\sum }_{i=1}^n,{|x_i-x_{i+1}|}^k\right)}^{1/k}=2^{1/k}·\sqrt{k}$. For the plane, the best constant is$$c_2=2$$ $c_2=2$and this is the only exact value known. Bollobás and Meir showed that one can take$$c_k = 9 \left( \frac{2}{3} \right) ^{1/k} \cdot \sqrt{k}$$ $c_k=9{\left(\frac{2}{3}\right)}^{1/k}·\sqrt{k}$for every$$k \ge 3$$ $k\ge 3$and conjectured that the best constant is$$c_k = 2^{1/k} \cdot \sqrt{k}$$ $c_k=2^{1/k}·\sqrt{k}$, for every$$k \ge 2$$ $k\ge 2$. Here we significantly improve the upper bound and show that one can take$$c_k = 3 \sqrt{5} \left( \frac{2}{3} \right) ^{1/k} \cdot \sqrt{k}$$ $c_k=3\sqrt{5}{\left(\frac{2}{3}\right)}^{1/k}·\sqrt{k}$or$$c_k = 2.91 \sqrt{k} \ (1+o_k(1))$$ $c_k=2.91\sqrt{k}(1+o_k\left(1\right))$. Our bounds are constructive. We also show that$$c_3 \ge 2^{7/6}$$ $c_3\ge 2^{7/6}$, which disproves the conjecture for$$k=3$$ $k=3$. Connections to matching problems, power assignment problems, related problems, including algorithms, are discussed in this context. A slightly revised version of the Bollobás–Meir conjecture is proposed. 

   more » « less
5. Size dependence- and induced transformations- of fractional quantum Hall effects under tilted magnetic fields

   https://doi.org/10.1038/s41598-022-22812-x  

   Wijewardena, U. Kushan; Nanayakkara, Tharanga R.; Kriisa, Annika; Reichl, Christian; Wegscheider, Werner; Mani, Ramesh G. (November 2022, Scientific Reports)

   Abstract Two-dimensional electron systems subjected to high transverse magnetic fields can exhibit Fractional Quantum Hall Effects (FQHE). In the GaAs/AlGaAs 2D electron system, a double degeneracy of Landau levels due to electron-spin, is removed by a small Zeeman spin splitting,$$g \mu _B B$$ $g{\mu }_{B}B$, comparable to the correlation energy. Then, a change of the Zeeman splitting relative to the correlation energy can lead to a re-ordering between spin polarized, partially polarized, and unpolarized many body ground states at a constant filling factor. We show here that tuning the spin energy can produce fractionally quantized Hall effect transitions that include both a change in$$\nu$$ $\nu$for the$$R_{xx}$$ $R_{\mathrm{xx}}$minimum, e.g., from$$\nu = 11/7$$ $\nu =11/7$to$$\nu = 8/5$$ $\nu =8/5$, and a corresponding change in the$$R_{xy}$$ $R_{\mathrm{xy}}$, e.g., from$$R_{xy}/R_{K} = (11/7)^{-1}$$ $R_{\mathrm{xy}}/R_K={(11/7)}^{-1}$to$$R_{xy}/R_{K} = (8/5)^{-1}$$ $R_{\mathrm{xy}}/R_K={(8/5)}^{-1}$, with increasing tilt angle. Further, we exhibit a striking size dependence in the tilt angle interval for the vanishing of the$$\nu = 4/3$$ $\nu =4/3$and$$\nu = 7/5$$ $\nu =7/5$resistance minima, including “avoided crossing” type lineshape characteristics, and observable shifts of$$R_{xy}$$ $R_{\mathrm{xy}}$at the$$R_{xx}$$ $R_{\mathrm{xx}}$minima- the latter occurring for$$\nu = 4/3, 7/5$$ $\nu =4/3,7/5$and the 10/7. The results demonstrate both size dependence and the possibility, not just of competition between different spin polarized states at the same$$\nu$$ $\nu$and$$R_{xy}$$ $R_{\mathrm{xy}}$, but also the tilt- or Zeeman-energy-dependent- crossover between distinct FQHE associated with different Hall resistances. 

   more » « less