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Many applications involving plasma-liquid interactions depend on the reactive processes occurring at the plasma-liquid interface. We report on a falling liquid film plasma reactor allowing for in situ optical absorption measurements of the time-dependence of the ferricyanide/ferrocyanide redox reactivity, complemented with ex situ measurement of the decomposition of formate. We found excellent agreement between the measured decomposition percentages and the diffusion-limited decomposition of formate by interfacial plasma-enabled reactions, except at high pH in thin liquid films, indicating the involvement of previously unexplored plasma-induced liquid phase chemistry enabled by long-lived reactive species. We also determined that high pH facilitates a reduction-favoring environment in ferricyanide/ferrocyanide redox solutions. In situ conversion measurements of a 1:1 ferricyanide/ferrocyanide redox mixture exceed the measured ex situ conversion and show that conversion of a 1:1 ferricyanide/ferrocyanide mixture is strongly dependent on film thickness. We identified three dominant processes: reduction faster than ms time scales for film thicknesses >100 µm, •OH-driven oxidation on time scales of <10 ms, and reduction on 15 ms time scales for film thickness <100 µm. We attribute the slow reduction and larger formate decomposition at high pH to HO2- formed from plasma-produced H2O2 enabled by the high pH at the plasma-liquid interface as confirmed experimentally and by computed reaction rates of HO2- with ferricyanide. Overall, this work demonstrates the utility of liquid film reactors in enabling the discovery of new plasma-interfacial chemistry and the utility of atmospheric plasmas for electrodeless electrochemistry., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

Many-body dispersion (MBD) is a powerful framework to treat van der Waals (vdW) dispersion interactions in density-functional theory and related atomistic modeling methods. Several independent implementations of MBD with varying degree of functionality exist across a number of electronic structure codes, which both limits the current users of those codes and complicates dissemination of new variants of MBD. Here, we develop and document libMBD, a library implementation of MBD that is functionally complete, efficient, easy to integrate with any electronic structure code, and already integrated in FHI-aims, DFTB+, VASP, Q-Chem, CASTEP, and Quantum ESPRESSO. libMBD is written in modern Fortran with bindings to C and Python, uses MPI/ScaLAPACK for parallelization, and implements MBD for both finite and periodic systems, with analytical gradients with respect to all input parameters. The computational cost has asymptotic cubic scaling with system size, and evaluation of gradients only changes the prefactor of the scaling law, with libMBD exhibiting strong scaling up to 256 processor cores. Other MBD properties beyond energy and gradients can be calculated with libMBD, such as the charge-density polarization, first-order Coulomb correction, the dielectric function, or the order-by-order expansion of the energy in the dipole interaction. Calculations on supramolecular complexes with MBD-corrected electronic structure methods and a meta-review of previous applications of MBD demonstrate the broad applicability of the libMBD package to treat vdW interactions., (© 2023 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Thermal stability and pressure-dependent changes are key to molecular crystals and their properties. The determination of their thermal properties from ab initio methods is, however, a challenging task. While the low-frequency phonon spectrum related to intermolecular vibrations remains difficult to describe, the Quasi-Harmonic Approximation (QHA) also induces for molecular crystals a significant volume deviation, which makes their thermal behavior ill-determined. To overcome these difficulties, we consider a pragmatic energy correction (EC) that has long been used for atomic crystals, and we presently report the first ever use for molecular crystals. Applying the QHA in dispersion-corrected density functional theory (DFT-D) calculations with an ab initio parameterized EC, the resulting model can simultaneously and accurately derive thermal and mechanical properties of high-explosive molecular crystals. When compared to experiments, the mean absolute percent error of previous DFT-based thermomechanical models is 12% for mechanical and 31% for thermal properties. Our model performs significantly better and reduces these uncertainties to 4.1% and 9.8%, respectively. In particular, the agreement between our model and experiments for the thermal properties is three times better. This significant improvement greatly benefits the determination of thermomechanical properties such as the Grüneisen parameter and the shock properties. The method has been successfully applied to molecular crystals showing a large diversity of weak intermolecular interactions (β-1,3,5,7-tetranitro-1,3,5,7-tetrazoctane (HMX), α-1,1-diamino-2,2-dinitroethylene (FOX-7), Triaminotrinitrobenzene (TATB), ε-Hexanitrohexaazaisowurtzitane (CL20), and Pentaerythritol tetranitrate (PETN)-I). Due to its accuracy and transferability, our model is expected to work for a large class of computationally designed molecular crystals and co-crystals, providing a basis for a predictive framework.

We present a mirrored atomistic and continuum framework that is used to describe the ignition of energetic materials, and a high-pressure phase of RDX in particular. The continuum formulation uses meaningful averages of thermodynamic properties obtained from the atomistic simulation and a simplification of enormously complex reaction kinetics. In particular, components are identified based on molecular weight bin averages and our methodology assumes that both the averaged atomistic and continuum simulations are represented on the same time and length scales. The atomistic simulations of thermally initiated ignition of RDX are performed using reactive molecular dynamics (RMD). The continuum model is based on multi-component thermodynamics and uses a kinetics scheme that describes observed chemical changes of the averaged atomistic simulations. Thus the mirrored continuum simulations mimic the rapid change in pressure, temperature, and average molecular weight of species in the reactive mixture. This mirroring enables a new technique to simplify the chemistry obtained from reactive MD simulations while retaining the observed features and spatial and temporal scales from both the RMD and continuum model. The primary benefit of this approach is a potentially powerful, but familiar way to interpret the atomistic simulations and understand the chemical events and reaction rates. The approach is quite general and thus can provide a way to model chemistry based on atomistic simulations and extend the reach of those simulations.

Electrocatalytic reduction of oxygen is composed of multiple steps, including the diffusion-adsorption-dissociation of molecular oxygen. This study explores the role of electrical double layer in aqueous medium in quantifying the rate of these coupled electrochemical processes at the electrode interface during oxygen reduction. The electronic, energetic, and configurational aspects of molecular oxygen diffusion and adsorption onto Cu(111) in water are identified through density functional theory based computations. The liquid phase on Cu(111) is modeled with hexagonal-ordered water bilayers, at two slightly different structures, with O-H bonds either facing the vacuum or the metal surface. The results indicate that the energetically preferred structure of water bilayers and adsorption configuration of O2 are different in cathodic and anodic potentials. The diffusion of O2 is found to be heavily hindered at the water/metal interface because of the ordering of water molecules in bilayers as compared to the bulk liquid. The unique correlations of diffusion and adsorption kinetics with water structure identified in this work can provide clues for improving oxygen reduction efficiency.

Coupling molecular scale reaction kinetics with macroscopic combustion behavior is critical to understanding the influences of intermediate chemistry on energy propagation, yet bridging this multi-scale gap is challenging. This study integrates ab initio quantum chemical calculations and condensed phase density functional theory to elucidate factors contributing to experimentally measured high flame speeds (i.e., >900 m∕s) associated with halogen based energetic composites, such as aluminum (Al) and iodine pentoxide (I2O5). Experiments show a direct correlation between apparent activation energy and flame speed suggesting that flame speed is directly influenced by chemical kinetics. Toward this end, the first principle simulations resolve key exothermic surface and intermediate chemistries contributing toward the kinetics that promote high flame speeds. Linking molecular level exothermicity to macroscopic experimental investigations provides insight into the unique role of the alumina oxide shell passivating aluminum particles. In the case of Al reacting with I2O5, the alumina shell promotes exothermic surface chemistries that reduce activation energy and increase flame speed. This finding is in contrast to Al reaction with metal oxides that show the alumina shell does not participate exothermically in the reaction.

The effect of particle size on combustion efficiency is an important factor in combustion research. Gas-phase aluminum clusters in oxidizing environment constitute a relatively simple and extensively studied system. In an attempt to underscore the correlation between electronic structure, finite size effect, and reactivity in small aluminum clusters, reactions between aluminum, [Al(13)](-) cluster, and Teflon decomposition fragments were studied using theoretical calculations at the density functional theoretical level. The unimolecular rate constants calculated using transition state and Rice-Ramsperger-Kassel-Marcus theory show that reactions with COF and CF(2) species with aluminum are faster than those involving CF(3) and COF(2). The results show that the kinetic barriers along different exothermic reaction channels correlate with the trends in HOMO(R)-HOMO(TS) (HOMO denotes highest occupied molecular orbital) energy gap and related shifts of the HOMO levels of reactants. Overall reactions involving carbonyl fluoride species (COF and COF(2)) lead to CO elimination and fluorination of the Al cluster. The CF(3)/CF(2) fragments lead to stable multicenter Al-C bond formation on the fluorinated Al cluster surface. Temperature-, energy-, and pressure-dependent rate constants are provided for extrapolating the expected reaction kinetics to conditions similar to known combustion reactions.

We have used reactive force field (ReaxFF) to investigate the mechanism of interaction of alanes on Al(111) surface. Our simulations show that, on the Al(111) surface, alanes oligomerize into larger alanes. In addition, from our simulations, adsorption of atomic hydrogen on Al(111) surface leads to the formation of alanes via H-induced etching of aluminum atoms from the surface. The alanes then agglomerate at the step edges forming stringlike conformations. The identification of these stringlike intermediates as a precursor to the bulk hydride phase allows us to explain the loss of resolution in surface IR experiments with increasing hydrogen coverage on single crystal Al(111) surface. This is in excellent agreement with the experimental works of Go et al. [E. Go, K. Thuermer, and J. E. Reutt-Robey, Surf. Sci. 437, 377 (1999)]. The mobility of alanes molecules has been studied using molecular dynamics and it is found that the migration energy barrier of Al(2)H(6) is 2.99 kcal/mol while the prefactor is D(0)=2.82 x 10(-3) cm(2)/s. We further investigated the interaction between an alane and an aluminum vacancy using classical molecular dynamics simulations. We found that a vacancy acts as a trap for alane, and eventually fractionates/annihilates it. These results show that ReaxFF can be used, in conjunction with ab initio methods, to study complex reactions on surfaces at both ambient and elevated temperature conditions.

Zinc oxide (ZnO) samples in the form of hexagonal-based bipyramids and particles of nanometer dimensions were synthesized through solvothermal route and characterized by x-ray diffraction and transmission electron microscopy. Positron annihilation experiments were performed to study the structural defects such as vacancies and surfaces in these nanosystems. From coincidence Doppler broadening measurements, the positron trapping sites were identified as Zn vacancies or Zn-O-Zn trivacancy clusters. The positron lifetimes, their relative intensities, and the Doppler broadened lineshape parameter S all showed characteristic changes across the nanobipyramid size corresponding to the thermal diffusion length of positrons. In large nanobipyramids, vacancies within the crystallites also trapped positrons and the effects of agglomeration of such vacancies due to increased temperatures of synthesis were reflected in the variation of the annihilation parameters with their base diameters. The sizes of the nanoparticles used were all in the limit of thermal diffusion length of positrons and the annihilation characteristics were in accordance with the decreasing contribution from surfaces with increasing particle size.

Nanostructures of ZnS, both particles and rods, were synthesized through solvothermal processes and characterized by x-ray diffraction and high resolution transmission electron microscopy. Positron lifetime and Doppler broadening measurements were made to study the features related to the defect nanostructures present in the samples. The nanocrystalline grain surfaces and interfaces, which trapped significant fractions of positrons, gradually disappeared during grain growth, as indicated by the decreasing fraction of orthopositronium atoms. The crystal vacancies present within the grains also trapped positrons. These vacancies further agglomerated into clusters during the thermal treatment given to effect grain growth. The positron lifetime was remarkably large at extremely small grain sizes (approximately 1.5 nm) and this was attributed to the occurrence of quantum confinement effects, as verified through optical absorption measurements. Positron lifetimes in ZnS nanorods increased with increasing content of cubic phase in the samples and this observation is assigned to the annihilation of positrons in sites with increased cubic unit cell volume. The Doppler broadened spectra also indicated qualitative changes consistent with these observations.