By considering the catalytic performance on the whole pathway of methane to ethylene, W©SiO2 is finally selected as the most active catalyst for the NCM, which has the lowest rate-determining barrier of 1.62 eV and the smallest free energy span (1.06 eV) of the overall catalytic cycle.In recent years there has been a rapid growth in the development and application of new stochastic methods in electronic structure. These methods are quite diverse, from many-body wave function techniques in real space or determinant space to being used to sum perturbative expansions. This growth has been spurred by the more favorable scaling with the number of electrons and often better parallelization over large numbers of central processing unit (CPU) cores or graphical processing units (GPUs) than for high-end non-stochastic wave function based methods. This special issue of the Journal of Chemical Physics includes 33 papers that describe recent developments and applications in this area. As seen from the articles in the issue, stochastic electronic structure methods are applicable to both molecules and solids and can accurately describe systems with strong electron correlation. This issue was motivated, in part, by the 2019 Telluride Science Research Center workshop on Stochastic Electronic Structure Methods that we organized. Below we briefly describe each of the papers in the special issue, dividing the papers into six subtopics.The high activity and selectivity of Fe-based heterogeneous catalysts toward a variety of reactions that require the breaking of strong bonds are offset in large part by their considerable instability with respect to oxidative deactivation. While it has been shown that the stability of Fe catalysts is considerably enhanced by alloying them with precious metals (even at the single-atom limit), rational design criteria for choosing such secondary metals are still missing. Since oxidative deactivation occurs due to the strong binding of oxygen to Fe and reduction by adsorbed hydrogen mitigates the deactivation, we propose here to use the binding affinity of oxygen and hydrogen adatoms as the basis for rational design. As it would also be beneficial to use cheaper secondary metals, we have scanned over a large subset of 3d-5d mid-to-late transition metal single atoms and computationally determined their effect on the oxygen and hydrogen adlayer binding as a function of chemical potential and adsorbate coverage. We further determine the underlying chemical origins that are responsible for these effects and connect them to experimentally tunable quantities. Our results reveal a reliable periodic trend wherein oxygen binding is weakened greatest as one moves right and down the periodic table. Hydrogen binding shows the same trend only at high (but relevant) coverages and otherwise tends to have its binding slightly increased in all systems. Trends with secondary metal coverage are also uncovered and connected to experimentally tunable parameters.Electron paramagnetic resonance (EPR) spectroscopy is used to address the remarkable persistence of the native Arrhenius dependence of the 2-aminopropanol substrate radical rearrangement reaction in B12-dependent ethanolamine ammonia-lyase (EAL) from Salmonella typhimurium from physiological to cryogenic (220 K) temperatures. Two-component TEMPOL spin probe mobility in the presence of 10 mM (0.08% v/v) 2-aminopropanol over 200-265 K demonstrates characteristic concentric aqueous-cosolvent mesodomain and protein-associated domain (PAD, hydration layer) solvent phases around EAL in the frozen solution. The mesodomain formed by the relatively small amount of 2-aminopropanol is highly confined, as shown by an elevated temperature for the order-disorder transition (ODT) in the PAD (230-235 K) and large activation energy for TEMPOL rotation. Addition of 2% v/v dimethylsulfoxide expands the mesodomain, partially relieves PAD confinement, and leads to an ODT at 205-210 K. The ODT is also manifested as a deviation of the temperature-dependence of the EPR amplitude of cob(II)alamin and the substrate radical, bound in the enzyme active site, from Curie law behavior. This is attributed to an increase in sample dielectric permittivity above the ODT at the microwave frequency of 9.5 GHz. The relatively high frequency dielectric response indicates an origin in coupled protein surface group-water fluctuations of the Johari-Goldstein β type that span spatial scales of ∼0.1-10 Å on temporal scales of 10-10-10-7 s. The orthogonal EPR spin probe rotational mobility and solvent dielectric measurements characterize features of EAL protein-solvent dynamical coupling and reveal that excess substrate acts as a fluidizing cryosolvent to enable native enzyme reactivity at cryogenic temperatures.Fluctuations affect nanoporous transport in complex and intricate ways, making optimization of the signal-to-noise ratio in artificial designs challenging. Here, we focus on the simplest nanopore system, where non-interacting particles diffuse through a pore separating reservoirs. We find that the concentration difference between both sides (akin to the osmotic pressure drop) exhibits fractional noise in time t with mean square average that grows as t1/2. This originates from the diffusive exchange of particles from one region to another. We fully rationalize this effect, with particle simulations and analytic solutions. We further infer the parameters (pore radius and pore thickness) that control this exotic behavior. As a consequence, we show that the number of particles within the pore also exhibits fractional noise. Such fractional noise is responsible for noise spectral density scaling as 1/f3/2 with frequency f, and we quantify its amplitude. Our theoretical approach is applicable to more complex nanoporous systems (for example, with adsorption within the pore) and drastically simplifies both particle simulations and analytic calculus.A widely used strategy for simulating the charge transfer between donor and acceptor electronic states in an all-atom anharmonic condensed-phase system is based on invoking linear response theory to describe the system in terms of an effective spin-boson model Hamiltonian. Extending this strategy to photoinduced charge transfer processes requires also taking into consideration the ground electronic state in addition to the excited donor and acceptor electronic states. In this paper, we revisit the problem of describing such nonequilibrium processes in terms of an effective three-state harmonic model. We do so within the framework of nonequilibrium Fermi’s golden rule (NE-FGR) in the context of photoinduced charge transfer in the carotenoid-porphyrin-C60 (CPC60) molecular triad dissolved in explicit tetrahydrofuran (THF). To this end, we consider different ways for obtaining a three-state harmonic model from the equilibrium autocorrelation functions of the donor-acceptor, donor-ground, and acceptor-ground energy gaps, as obtained from all-atom molecular dynamics simulations of the CPC60/THF system. The quantum-mechanically exact time-dependent NE-FGR rate coefficients for two different charge transfer processes in two different triad conformations are then calculated using the effective three-state model Hamiltonians as well as a hierarchy of more approximate expressions that lead to the instantaneous Marcus theory limit. Our results show that the photoinduced charge transfer in CPC60/THF can be described accurately by the effective harmonic three-state models and that nuclear quantum effects are small in this system.Transition metal oxides (TMOs) are an important class of materials with diverse applications, ranging from memristors to photoelectrochemical cells. First-principles calculations are critical for understanding these complex materials at an atomic level and establishing relationships between atomic and electronic structures, particularly for probing quantities difficult or inaccessible to experiment. Here, we discuss computational strategies used to understand TMOs by focusing on two examples, a photoanode material, BiVO4, and an oxide for low-power electronics, La1-xSrxCoO3. We highlight key aspects required for the modeling of TMOs, namely, the descriptions of how oxygen vacancies, extrinsic doping, the magnetic state, and polaron formation impact their electronic and atomic structures and, consequently, many of the observed properties.A dynamical process that takes a random time to complete, e.g., a chemical reaction, may either be accelerated or hindered due to resetting. Tuning system parameters, such as temperature, viscosity, or concentration, can invert the effect of resetting on the mean completion time of the process, which leads to a resetting transition. Although the resetting transition has been recently studied for diffusion in a handful of model potentials, it is yet unknown whether the results follow any universality in terms of well-defined physical parameters. To bridge this gap, we propose a general framework that reveals that the resetting transition is governed by an interplay between the thermal and potential energy. This result is illustrated for different classes of potentials that are used to model a wide variety of stochastic processes with numerous applications.Cathodes are critical components of rechargeable batteries. Conventionally, the search for cathode materials relies on experimental trial-and-error and a traversing of existing computational/experimental databases. While these methods have led to the discovery of several commercially viable cathode materials, the chemical space explored so far is limited and many phases will have been overlooked, in particular, those that are metastable. We describe a computational framework for battery cathode exploration based on ab initio random structure searching (AIRSS), an approach that samples local minima on the potential energy surface to identify new crystal structures. We show that by delimiting the search space using a number of constraints, including chemically aware minimum interatomic separations, cell volumes, and space group symmetries, AIRSS can efficiently predict both thermodynamically stable and metastable cathode materials. Specifically, we investigate LiCoO2, LiFePO4, and LixCuyFz to demonstrate the efficiency of the method by rediscovering the known crystal structures of these cathode materials. The effect of parameters, such as minimum separations and symmetries, on the efficiency of the sampling is discussed in detail. The adaptation of the minimum interatomic distances on a species-pair basis, from low-energy optimized structures to efficiently capture the local coordination environment of atoms, is explored. A family of novel cathode materials based on the transition-metal oxalates is proposed. They demonstrate superb energy density, oxygen-redox stability, and lithium diffusion properties. This article serves both as an introduction to the computational framework and as a guide to battery cathode material discovery using AIRSS.We investigate the validity of the classical approximation to the numerically exact quantum dynamics for infrared laser-driven control of isomerization processes. To this end, we simulate the fully quantum mechanical dynamics both by wavepacket propagation in position space and by propagating the Wigner function in phase space employing a quantum-mechanical correction term. A systematic comparison is made with purely classical propagation of the Wigner function. On the example of a one-dimensional double well potential, we identify two complementary classes of pulse sequences that invoke either a quantum mechanically or a classically dominated control mechanism. The quantum control relies on a sequence of excitations and de-excitations between the system’s eigenstates on a time scale far exceeding the characteristic vibrational oscillation periods. In contrast, the classical control mechanism is based on a short and strong few-cycle field exerting classical-like forces driving the wavepacket to the target potential well where it is slowed down and finally trapped.