Notes

Phylogenomic connections and also famous biogeography within the Southerly American veggie ivory palm trees (Phytelepheae).
We find that the thermodynamic efficiency of this machine is zero because the field for the isothermal processes acts as a refrigerator, whereas that for the adiabatic wall acts as a heat engine. This is a numerical manifestation of the Kelvin-Planck statement, which states that it is impossible to derive the mechanical effects from a single heat source. These HEOM simulations serve as a rigorous test of thermodynamic formulations because the second law of thermodynamics is only valid when the work involved in the operation of the adiabatic wall is treated accurately.Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. However, for electronic systems with spin degrees of freedom, there are few if any applicable and practical quasiclassical methods. Here, we show that for nonadiabatic dynamics with two electronic states and a complex-valued Hamiltonian that does not obey time-reversal symmetry (as relevant to many coupled nuclear-electronic-spin systems), the optimal semiclassical approach is to generalize Tully's surface hopping dynamics from coordinate space to phase space. In order to generate the relevant phase-space adiabatic surfaces, one isolates a proper set of diabats, applies a phase gauge transformation, and then diagonalizes the total Hamiltonian (which is now parameterized by both R and P). The resulting algorithm is simple and valid in both the adiabatic and nonadiabatic limits, incorporating all Berry curvature effects. Most importantly, the resulting algorithm allows for the study of semiclassical nonadiabatic dynamics in the presence of spin-orbit coupling and/or external magnetic fields. One expects many simulations to follow as far as modeling cutting-edge experiments with entangled nuclear, electronic, and spin degrees of freedom, e.g., experiments displaying chiral-induced spin selectivity.Based on 280 reference vertical transition energies of various excited states (singlet, triplet, valence, Rydberg, n → π*, π → π*, and double excitations) extracted from the QUEST database, we assess the accuracy of complete-active-space third-order perturbation theory (CASPT3), in the context of molecular excited states. When one applies the disputable ionization-potential-electron-affinity (IPEA) shift, we show that CASPT3 provides a similar accuracy as its second-order counterpart, CASPT2, with the same mean absolute error of 0.11 eV. However, as already reported, we also observe that the accuracy of CASPT3 is almost insensitive to the IPEA shift, irrespective of the transition type and system size, with a small reduction in the mean absolute error to 0.09 eV when the IPEA shift is switched off.We demonstrate the first phase stable measurement of a third-order 2Q spectrum using a pulse shaper in the pump-probe geometry. This measurement was achieved by permuting the time-ordering of the pump pulses, thus rearranging the signal pathways that are emitted in the probe direction. The third-order 2Q spectrum is self-heterodyned by the probe pulse. Using this method, one can interconvert between a 1Q experiment and a 2Q experiment by simply reprogramming a pulse shaper or delay stage. We also measure a fifth-order absorptive 2Q spectrum in the pump-probe geometry, which contains similar information as a third-order experiment but does not suffer from dispersive line shapes. To do so, we introduce methods to minimize saturation-induced artifacts of the pulse shaper, improving fifth-order signals. These techniques add new capabilities for 2D spectrometers that use pulse shapers in the pump-probe beam geometry.Propulsion of otherwise passive objects is achieved by mechanisms of active driving. We concentrate on cases in which the direction of active drive is subject to spontaneous symmetry breaking. In our case, this direction will be maintained until a large enough impulse by an additional stochastic force reverses it. Examples may be provided by self-propelled droplets, gliding bacteria stochastically reversing their propulsion direction, or nonpolar vibrated hoppers. The magnitude of active forcing is regarded as constant, and we include the effect of inertial contributions. Interestingly, this situation can formally be mapped to stochastic motion under (dry, solid) Coulomb friction, however, with a negative friction parameter. Diffusion coefficients are calculated by formal mapping to the situation of a quantum-mechanical harmonic oscillator exposed to an additional repulsive delta-potential. Results comprise a ditched or double-peaked velocity distribution and spatial statistics showing outward propagating maxima when starting from initially concentrated arrangements.The glass formation ability of an alloy depends on two competing processes glass-transition, on one hand, and crystal nucleation and growth, on the other hand. While these phenomena have been widely studied before in nearly equiatomic Cu-Zr alloys, studies are lacking for solute/solvent-rich ones. In the present work, molecular dynamics simulations show that the addition of a small amount of Zr (1-10 at. %) to Cu drastically increases the incubation time and slows down crystal growth, thus, leading to an improved glass forming ability. The crystal nucleation and growth processes of a competing face-centered cubic (FCC) Cu crystalline phase are analyzed in detail. In particular, the values of the critical cooling rate, incubation period for crystallization, and growth rate of FCC Cu crystals in these Cu-rich alloys are obtained. The growth of a supersaturated FCC Cu solid solution is found to be polymorphic at the interface (except for alloys with 9 and 10 at. % Zr) though a Zr concentration gradient is observed within growing crystals at high enough Zr content. The crystal growth rate before crystal impingement is nearly constant in all alloys, though it decreases exponentially with the Zr content. Crystallization kinetics are also analyzed within the existing theories and compared with the experimental values available in the literature.The prediction of the thermodynamic and kinetic properties of chemical reactions is increasingly being addressed by machine-learning (ML) methods, such as artificial neural networks (ANNs). While a number of recent studies have reported success in predicting chemical reaction activation energies, less attention has been focused on how the accuracy of ML predictions filters through to predictions of macroscopic observables. Here, we consider the impact of the uncertainty associated with ML prediction of activation energies on observable properties of chemical reaction networks, as given by microkinetics simulations based on ML-predicted reaction rates. check details After training an ANN to predict activation energies, given standard molecular descriptors for reactants and products alone, we performed microkinetics simulations of three different prototypical reaction networks formamide decomposition, aldol reactions, and decomposition of 3-hydroperoxypropanal. We find that the kinetic modeling predictions can be in excellent agreement with corresponding simulations performed with ab initio calculations, but this is dependent on the inherent energetic landscape of the networks. We use these simulations to suggest some guidelines for when ML-based activation energies can be reliable and when one should take more care in applications to kinetics modeling.Active systems, which are driven out of equilibrium by local non-conservative forces, exhibit unique behaviors and structures with potential utility for the design of novel materials. An important and difficult challenge along the path toward this goal is to precisely predict how the structure of active systems is modified as their driving forces push them out of equilibrium. Here, we use tools from liquid-state theories to approach this challenge for a classic minimal active matter model. First, we construct a nonequilibrium mean-field framework that can predict the structure of systems of weakly interacting particles. Second, motivated by equilibrium solvation theories, we modify this theory to extend it with surprisingly high accuracy to systems of strongly interacting particles, distinguishing it from most existing similarly tractable approaches. Our results provide insight into spatial organization in strongly interacting out-of-equilibrium systems.The pulsed-laser photolysis/laser-induced fluorescence method is used to study the kinetics of the reaction of NH2 with H2O2 to yield a second-order rate constant of (2.42 ± 0.55) × 10-14 cm3 molecule-1 s-1 at 412 K in 10-22 mbar of Ar bath gas. There are no prior measurements for comparison. To check this value and enable reliable extrapolation to other temperatures, we also compute thermal rate constants for this process over the temperature range 298-3000 K via multi-structural canonical variational transition-state theory with small-curvature multidimensional tunneling (MS-CVT/SCT). The CVT/SCT rate constants are derived using a dual-level direct dynamics approach utilizing single-point CCSD(T)-F12b/cc-pVQZ-F12 energies-corrected for core-valence and scalar relativistic effects-and M06-2X/MG3S geometries, gradients, and Hessians-for all stationary and non-stationary points along the reaction path. The multistructural method with torsional anharmonicity, based on a coupled torsional potential, is then employed to calculate correction factors for the rate constants, accounting for the comprehensive effects of torsional anharmonicity on the kinetics of this reaction system. The final MS-CVT/SCT rate constants are found to be in good agreement with our measurements and can be expressed in modified Arrhenius form as 2.13 × 10-15 (T/298 K)4.02 exp(-513 K/T) cm3 molecule-1 s-1 over the temperature range of 298-3000 K.The anharmonic properties of the longitudinal optical (LO) phonon mode of Mg-doped ZnS (Zn0.96 Mg0.04S) are investigated using the Balkanski and Klemens models on the temperature-dependent Raman spectra. The variation in the position of the Raman line, peak width, and phonon lifetime with temperature was fitted using three and four phonon decay mechanisms. The values of the anharmonic fitting parameters indicated low anharmonicity. A lifetime of ∼0.17 ps at 90 K indicated a fast phonon decay. In addition, the thin film is analyzed to evaluate its surface characteristics using Raman mapping that showed chemical homogeneity over a large area of the film. Furthermore, we analyzed spatial variations of Raman line intensity, peak area, linewidth, and line position of the LO phonon mode. Raman analysis helped in understanding the phonon-phonon interaction mechanism in Zn0.96 Mg0.04S thin films.The intramolecular vibrational relaxation dynamics of formic acid and its deuterated isotopologues is simulated on the full-dimensional potential energy surface of Richter and Carbonnière [J. Chem. Phys. 148, 064303 (2018)] using the Heidelberg MCTDH package. We focus on couplings with the torsion vibrational modes close to the trans-cis isomerization coordinate from the dynamics of artificially excited vibrational mode overtones. The bright C-O stretch vibrational mode is coupled to the out-of-the plane torsion mode in HCOOH, where this coupling could be exploited for laser-induced trans-to-cis isomerization. Strong isotopic effects are observed deuteration of the hydroxyl group, i.e., in HCOOD and DCOOD, destroys the C-O stretch to torsion mode coupling whereas in DCOOH, little to no effect is observed.
Website: https://www.selleckchem.com/products/d-lin-mc3-dma.html