Low-Hydrophilic HKUST-1/Polymer Extrudates for the PSA Separation of CO2/CH4.

HKUST-1 is an MOF adsorbent industrially produced in powder form and thus requires a post-shaping process for use as an adsorbent in fixed-bed separation processes. HKUST-1 is also sensitive to moisture, which degrades its crystalline structure. In this work, HKUST-1, in the form of crystalline powder, was extruded into pellets using a hydrophobic polymeric binder to improve its moisture stability. Thermoplastic polyurethane (TPU) was used for that purpose. The subsequent HKUST-1/TPU extrudate was then compared to HKUST-1/PLA extrudates synthesized with more hydrophilic polymer: polylactic acid (PLA), as the binder. The characterization of the composites was determined via XRD, TGA, SEM-EDS, and an N2 adsorption isotherm analysis. Meanwhile, the gas-separation performances of HKUST-1/TPU were investigated and compared with HKUST-1/PLA from measurements of CO2 and CH4 isotherms at three different temperatures, up to 10 bars. Lastly, the moisture stability of the composite materials was investigated via an aging analysis during storage under humid conditions. It is shown that HKUST-1's crystalline structure was preserved in the HKUST-1/TPU extrudates. The composites also exhibited good thermal stability under 523 K, whilst their textural properties were not significantly modified compared with the pristine HKUST-1. Furthermore, both extrudates exhibited larger CO2 and CH4 adsorption capacities in comparison to the pristine HKUST-1. After three months of storage under atmospheric humid conditions, CO2 adsorption capacities were reduced to only 10% for HKUST-1/TPU, whereas reductions of about 25% and 54% were observed for HKUST-1/PLA and the pristine HKUST-1, respectively. This study demonstrates the interest in shaping MOF powders by extrusion using a hydrophobic thermoplastic binder to operate adsorbents with enhanced moisture stability in gas-separation columns.

Tuning Surface Defect States in Sputtered Titanium Oxide Electron Transport Layers for Enhanced Stability of Organic Photovoltaics.

Nonfullerene acceptors (NFAs) have dramatically improved the power conversion efficiency (PCE) of organic photovoltaics (OPV) in recent years; however, their device stability currently remains a bottleneck for further technological progress. Photocatalytic decomposition of nonfullerene acceptor molecules at metal oxide electron transport layer (ETL) interfaces has in several recent reports been demonstrated as one of the main degradation mechanisms for these high-performing OPV devices. While some routes for mitigating such degradation effects have been proposed, e.g., through a second layer integrated on the ETL surface, no clear strategy that complies with device scale-up and application requirements has been presented to date. In this work, it is demonstrated that the development of sputtered titanium oxide layers as ETLs in nonfullerene acceptor based OPV can lead to significantly enhanced device lifetimes. This is achieved by tuning the concentration of defect states at the oxide surface, via the reactive sputtering process, to mitigate the photocatalytic decomposition of NFA molecules at the metal oxide interlayers. Reduced defect state formation at the oxide surface is confirmed through X-ray photoelectron spectroscopy (XPS) studies, while the reduced photocatalytic decomposition of nonfullerene acceptor molecules is confirmed via optical spectroscopy investigations. The PBDB-T:ITIC organic solar cells show power conversion efficiencies of around 10% and significantly enhanced photostability. This is achieved through a reactive sputtering process that is fully scalable and industry compatible.

Positivity preserving density matrix minimization at finite temperatures via square root.

We present a Wave Operator Minimization (WOM) method for calculating the Fermi-Dirac density matrix for electronic structure problems at finite temperature while preserving physicality by construction using the wave operator, i.e., the square root of the density matrix. WOM models cooling a state initially at infinite temperature down to the desired finite temperature. We consider both the grand canonical (constant chemical potential) and canonical (constant number of electrons) ensembles. Additionally, we show that the number of steps required for convergence is independent of the number of atoms in the system. We hope that the discussion and results presented in this article reinvigorate interest in density matrix minimization methods.

Superoscillations Deliver Superspectroscopy.

In ordinary circumstances the highest frequency present in a wave is the highest frequency in its Fourier decomposition. It is however possible for there to be a spatial or temporal region where the wave locally oscillates at a still greater frequency in a phenomenon known as superoscillation. Superoscillations find application in wide range of disciplines, but at present their generation is based upon constructive approaches that are difficult to implement. Here, we address this, exploiting the fact that superoscillations are a product of destructive interference to produce a prescription for generating superoscillations from the superposition of arbitrary waveforms. As a first test of the technique, we use it to combine four quasisinusoidal THz waveforms to produce THz optical superoscillations for the first time. The ability to generate superoscillations in this manner has potential application in a wide range of fields, which we demonstrate with a method we term "superspectroscopy." This employs the generated superoscillations to obtain an observed enhancement of almost an order of magnitude in the spectroscopic sensitivity to materials whose resonance lies outside the range of the component waveform frequencies.

Combining experiments on luminescent centres in hexagonal boron nitride with the polaron model and ab initio methods towards the identification of their microscopic origin.

The two-dimensional material hexagonal boron nitride (hBN) hosts luminescent centres with emission energies of ∼2 eV which exhibit pronounced phonon sidebands. We investigate the microscopic origin of these luminescent centres by combining ab initio calculations with non-perturbative open quantum system theory to study the emission and absorption properties of 26 defect transitions. Comparing the calculated line shapes with experiments we narrow down the microscopic origin to three carbon-based defects: C2CB, C2CN, and VNCB. The theoretical method developed enables us to calculate so-called photoluminescence excitation (PLE) maps, which show excellent agreement with our experiments. The latter resolves higher-order phonon transitions, thereby confirming both the vibronic structure of the optical transition and the phonon-assisted excitation mechanism with a phonon energy ∼170 meV. We believe that the presented experiments and polaron-based method accurately describe luminescent centres in hBN and will help to identify their microscopic origin.

Molybdenum Disulfide Nanoribbons with Enhanced Edge Nonlinear Response and Photoresponsivity.

MoS2 nanoribbons have attracted increased interest due to their properties, which can be tailored by tuning their dimensions. Herein, the growth of MoS2 nanoribbons and triangular crystals formed by the reaction between films of MoOx (2

A facile strategy for the growth of high-quality tungsten disulfide crystals mediated by oxygen-deficient oxide precursors.

Chemical vapor deposition (CVD) has been established as a versatile route for the large-scale synthesis of transition metal dichalcogenides, such as tungsten disulfide (WS2). Yet, the precursor composition's role on the CVD process remains largely unknown and remains to be explored. Here, we employ Pulsed Laser Deposition (PLD) in a two-stage approach to tune the oxygen content in the tungsten oxide (WO3-x) precursors and demonstrate the presence of oxygen vacancies in the oxide films leads to a more facile conversion from WO3-x to WS2. Using a joint study based on ab initio density functional theory (DFT) calculations and experimental observations, we unravel that the oxygen vacancies in WO3-x can serve as niches through which sulfur atoms enter the lattice and facilitate an efficient conversion into WS2 crystals. By solely modulating the precursor stoichiometry, the photoluminescence emission of WS2 crystals can be significantly enhanced. Atomic resolution scanning transmission electron microscopy imaging (STEM) reveals that tungsten vacancies are the dominant intrinsic defects in mono- and bilayers WS2. Moreover, bi- and multilayer WS2 crystals derived from oxides with a high V0 content exhibit dominant AA'/AB or AA(A…) stacking orientations. The atomic resolution images reveal local strain buildup in bilayer WS2 due to competing effects of complex grain boundaries. Our study provides means to tune the precursor composition to control the lateral growth of TMDs while revealing insights into the different pathways for forming grain boundaries in bilayer WS2.

Optical Indistinguishability via Twinning Fields.

Here we introduce the concept of the twinning field-a driving electromagnetic pulse that induces an identical optical response from two distinct materials. We show that for a large class of pairs of generic many-body systems, a twinning field which renders the systems optically indistinguishable exists. The conditions under which this field exists are derived, and this analysis is supplemented by numerical calculations of twinning fields for both the 1D Fermi-Hubbard model, and tight-binding models of graphene and hexagonal boron nitride. The existence of twinning fields may lead to new research directions in nonlinear optics, materials science, and quantum technologies.

Explicit volume-preserving numerical schemes for relativistic trajectories and spin dynamics.

A class of explicit numerical schemes is developed to solve for the relativistic dynamics and spin of particles in electromagnetic fields, using the Lorentz-Bargmann-Michel-Telegdi equation formulated in the Clifford algebra representation of Baylis. It is demonstrated that these numerical methods, reminiscent of the leapfrog and Verlet methods, share a number of important properties: they are energy conserving, volume conserving, and second-order convergent. These properties are analyzed empirically by benchmarking against known analytical solutions in constant uniform electrodynamic fields. It is demonstrated that the numerical error in a constant magnetic field remains bounded for long-time simulations in contrast to the Boris pusher, whose angular error increases linearly with time. Finally, the intricate spin dynamics of a particle is investigated in a plane-wave field configuration.

Robust polarimetry via convex optimization.

We present mathematical methods, based on convex optimization, for correcting non-physical coherency matrices measured in polarimetry. We also develop the method for recovering the coherency matrices corresponding to the smallest and largest values of the degree of polarization given the experimental data and a specified tolerance. We use experimental non-physical results obtained with the standard polarimetry scheme and a commercial polarimeter to illustrate these methods. Our techniques are applied in post-processing, which complements other experimental methods for robust polarimetry.

Thermodynamic data of adsorption reveal the entry of CH4 and CO2 in a smectite clay interlayer.

The ability of smectite clays to incorporate gases in their interlayers is shown to be conditioned by interlayer spacing, depending, in turn, on phyllosilicate layer composition and effective size of the charge-balancing cations. As illustrated by earlier in situ X-ray diffraction and spectroscopic characterization of the gas/clay interface, most smectites with small-size charge-balancing cations, such as Na+ or Ca2+, accommodate CO2 and CH4 in their interlayers only in a partially hydrated state resulting in the opening of the basal spacing, above a certain critical value. In the present study CH4 and CO2 adsorption isotherms were measured for Na- and Mg-exchanged montmorillonite up to 9 MPa using a manometric technique. The process of dehydration of these clays was thoroughly characterized by thermogravimetric analysis and powder X-ray diffraction. A dramatic decrease in specific surface area and methane and carbon dioxide adsorption capacities for fully dehydrated samples in comparison to partially dehydrated ones is assigned to the shrinkage of interlayer spacing resulting in its inaccessibility for the entry of CH4 and CO2 molecules. This observation is direct evidence of CH4 and CO2 adsorption capacity variation depending on the opening of smectite clay interlayer spacing.

Driven Imposters: Controlling Expectations in Many-Body Systems.

We present a framework for controlling the observables of a general correlated electron system driven by an incident laser field. The approach provides a prescription for the driving required to generate an arbitrary predetermined evolution for the expectation value of a chosen observable, together with a constraint on the maximum size of this expectation. To demonstrate this, we determine the laser fields required to exactly control the current in a Fermi-Hubbard system under a range of model parameters, fully controlling the nonlinear high-harmonic generation and optically observed electron dynamics in the system. This is achieved for both the uncorrelated metalliclike state and deep in the strongly correlated Mott insulating regime, flipping the optical responses of the two systems so as to mimic the other, creating "driven imposters." We also present a general framework for the control of other dynamical variables, opening a new route for the design of driven materials with customized properties.

Combining Lindblad Master Equation and Surface Hopping to Evolve Distributions of Quantum Particles.

Motivated by the need to study nonequilibrium evolutions of many-electron systems at the atomistic ab initio level, as they occur in modern devices and applications, we developed a quantum dynamics approach bridging master equations and surface hopping (SH). The Lindblad master equation (LME) allows us to propagate efficiently ensembles of particles, while SH provides nonperturbative evaluation of transition rates that evolve in time and depend explicitly on nuclear geometry. We implemented the LME-SH technique within real-time time-dependent density functional theory using global flux SH, and we demonstrated its efficiency and utility by modeling metallic films, in which charge-phonon dynamics was studied experimentally and showed an unexpectedly strong dependence on adhesion layers. The LME-SH approach provides a general framework for modeling efficiently quantum dynamics in a broad range of complex many-electron condensed-matter and nanoscale systems.

Uncomputability and complexity of quantum control.

In laboratory and numerical experiments, physical quantities are known with a finite precision and described by rational numbers. Based on this, we deduce that quantum control problems both for open and closed systems are in general not algorithmically solvable, i.e., there is no algorithm that can decide whether dynamics of an arbitrary quantum system can be manipulated by accessible external interactions (coherent or dissipative) such that a chosen target reaches a desired value. This conclusion holds even for the relaxed requirement of the target only approximately attaining the desired value. These findings do not preclude an algorithmic solvability for a particular class of quantum control problems. Moreover, any quantum control problem can be made algorithmically solvable if the set of accessible interactions (i.e., controls) is rich enough. To arrive at these results, we develop a technique based on establishing the equivalence between quantum control problems and Diophantine equations, which are polynomial equations with integer coefficients and integer unknowns. In addition to proving uncomputability, this technique allows to construct quantum control problems belonging to different complexity classes. In particular, an example of the control problem involving a two-mode coherent field is shown to be NP-hard, contradicting a widely held believe that two-body problems are easy.

Koopman wavefunctions and classical-quantum correlation dynamics.

Upon revisiting the Hamiltonian structure of classical wavefunctions in Koopman-von Neumann theory, this paper addresses the long-standing problem of formulating a dynamical theory of classical-quantum coupling. The proposed model not only describes the influence of a classical system onto a quantum one, but also the reverse effect-the quantum backreaction. These interactions are described by a new Hamiltonian wave equation overcoming shortcomings of currently employed models. For example, the density matrix of the quantum subsystem is always positive definite. While the Liouville density of the classical subsystem is generally allowed to be unsigned, its sign is shown to be preserved in time for a specific infinite family of hybrid classical-quantum systems. The proposed description is illustrated and compared with previous theories using the exactly solvable model of a degenerate two-level quantum system coupled to a classical harmonic oscillator.

Entropy nonconservation and boundary conditions for Hamiltonian dynamical systems.

Applying the theory of self-adjoint extensions of Hermitian operators to Koopman von Neumann classical mechanics, the most general set of probability distributions is found for which entropy is conserved by Hamiltonian evolution. A new dynamical phase associated with such a construction is identified. By choosing distributions not belonging to this class, we produce explicit examples of both free particles and harmonic systems evolving in a bounded phase-space in such a way that entropy is nonconserved. While these nonconserving states are classically forbidden, they may be interpreted as states of a quantum system tunneling through a potential barrier boundary. In this case, the allowed boundary conditions are the only distinction between classical and quantum systems. We show that the boundary conditions for a tunneling quantum system become the criteria for entropy preservation in the classical limit. These findings highlight how boundary effects drastically change the nature of a system.

Nonconservative Forces via Quantum Reservoir Engineering.

A systematic approach is given for engineering dissipative environments that steer quantum wave packets along desired trajectories. The methodology is demonstrated with several illustrative examples: environment-assisted tunneling, trapping, effective mass assignment, and pseudorelativistic behavior. Nonconservative stochastic forces do not inevitably lead to decoherence-we show that purity can be well preserved. These findings highlight the flexibility offered by nonequilibrium open quantum dynamics.

No Thermalization without Correlations.

The proof of the long-standing conjecture is presented that Markovian quantum master equations are at odds with quantum thermodynamics under conventional assumptions of fluctuation-dissipation theorems (implying a translation invariant dissipation). Specifically, except for identified systems, persistent system-bath correlations of at least one kind, spatial or temporal, are obligatory for thermalization. A systematic procedure is proposed to construct translation invariant bath models producing steady states that well approximate thermal states. A quantum optical scheme for the laboratory assessment of the developed procedure is outlined.

Analytic Solutions to Coherent Control of the Dirac Equation.

A simple framework for Dirac spinors is developed that parametrizes admissible quantum dynamics and also analytically constructs electromagnetic fields, obeying Maxwell's equations, which yield a desired evolution. In particular, we show how to achieve dispersionless rotation and translation of wave packets. Additionally, this formalism can handle control interactions beyond electromagnetic. This work reveals unexpected flexibility of the Dirac equation for control applications, which may open new prospects for quantum technologies.