Functional Groups Assisted Tunable Dielectric Permittivity of Guest-Free Zn-Based Coordination Polymers for Gate Dielectrics

The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH₂) and electron-withdrawing (R=NO₂) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L₁)(L₂)]_n ( 1 ) and [Zn(L₁)(L₃)]_n ( 2 ) [L₁=2-(2-pyridyl) benzimidazole (Pbim), L₂=5-aminoisophthalate (Aip), and L₃=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH₂ and NO₂ substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO₂ and NH₂. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties.     

Atom—Field Correlations in the Weak-Excitation Limit of Absorptive Optical Bistability

We calculate the steady-state and first-order time varying atom—field correlation functions in the weak-excitation limit of absorptive optical bistability from a linearized theory of quantum fluctuations. We formulate a Fokker—Planck equation in the positive P representation following the phase-space analysis in [H. J. Carmichael, Phys. Rev. A 33, 3262 (1986)], which is suitable for the determination of cross-correlations as it does not resort to adiabatic elimination. Special emphasis is placed on the limit of collective strong coupling as attained from a vanishing photon-loss rate. We compare to the cavity-transmission spectrum with reference to experimental results obtained for macroscopic dissipative systems, discussing the role of anomalous correlations arising as distinct nonclassical features.

     

Dynamically Induced Excitonic Instability in Pumped Dirac Materials

Driven and non-equilibrium quantum states of matter have attracted growing interest in both theoretical and experimental studies in condensed matter physics. Recent progress in realizing transient collective states in driven or pumped Dirac materials (DMs) is reviewed herein. In particular, the focus is on optically pumped DMs which are a promising platform for transient excitonic instabilities. Optical pumping combined with the linear (Dirac) dispersion of the electronic spectrum offers a knob for tuning the effective interaction between the photoexcited electrons and holes, and thus provides a way of reducing the critical coupling for excitonic instability. As a result, a transient excitonic condensate could be achieved in a pumped DM while it is not feasible in equilibrium. A unifying theoretical framework is provided for describing transient collective states in 2D and 3D DMs. The experimental signatures are described and numerical estimates of the size of the dynamically induced excitonic gaps and the values of the critical temperatures for several specific systems, are summarized. In addition, general guidelines for identifying promising material candidates are discussed. Finally, comments are provided regarding recent experimental efforts in realizing transient excitonic condensate in pumped DMs, and outstanding issues and possible future directions are outlined.     

Triplet P states in Ps− using correlated exponential wave functions

We calculate the resonance parameters (energy and width) for the doubly excited ³P^o and ³P^e states in Ps⁻ using correlated exponential wave functions. The calculations are based on the method of complex-coordinate rotation. The resonance energies and widths for the triplet P-wave Feshbach and shape resonances with both even and odd parities in Ps⁻ ion associated with the N = 2, 3, 4, 5 Ps thresholds are reported. Our predications are in agreement with the available results. Few Feshbach and shape resonance parameters are reported for the first time in the literature. In view of a recent experiment on a singlet P-wave shape resonance state in Ps⁻, it is highly expected that the predications obtained from this study for the triplet P-wave resonance states will provide useful information for the future resonance experiments in Ps⁻. Furthermore, our findings could be found useful for the research communities of atomic physics, nuclear physics, and semiconductor quantum dots including excitons.     

Intrinsic electrochemical performance and precise control of surface porosity of graphene-modified electrodes using the drop-casting technique

Graphenes have for a long time been shown to exhibit enhanced electrochemical sensing and fast heterogeneous electron transfers, but the nature of such improved electrochemistry is disputed due to its inherent porosity. Adsorption and thin layer effects may additionally contribute to the observed behaviour. Furthermore, overall extents of the impact from these factors are typically unclear. Towards a practical solution to this issue, we show that electrode porosity can be adequately controlled close to the case of an ideal planar electrode. With increased mass loadings, the apparent porosity can still be precisely controlled by performing multiple drop-casts from less concentrated dispersions. Thus with application of such experimental practices, the drop-casting technique remains a reliable option for nanomaterial electrode preparation.     

Solvent‐Dependent Structure of the I3− Ion Derived from Photoelectron Spectroscopy and Ab Initio Molecular Dynamics Simulations

Ab initio molecular dynamics (MD) simulations of the solvation of LiI₃ in four different solvents (water, methanol, ethanol, and acetonitrile) are employed to investigate the molecular and electronic structure of the I₃^? ion in relation to X‐ray photoelectron spectroscopy (XPS). Simulations show that hydrogen‐bond rearrangement in the solvation shell is coupled to intramolecular bond‐length asymmetry in the I₃^? ion. By a combination of charge analysis and I 4 d core‐level XPS measurements, the mechanism of the solvent‐induced distortions has been studied, and it has been concluded that charge localization mediates intermolecular interactions and intramolecular distortion. The approach involving a synergistic combination of theory and experiment probes the solvent‐dependent structure of the I₃^? ion, and the geometric structure has been correlated with the electronic structure.