Cluster Amplitudes and Their Interplay with Self-Consistency in Density Functional Methods.

The front cover artwork is provided by the Mosquera group at Montana State University, Bozeman. The image shows theoretical elements involved in the density-functional calculations that are free of spurious fractional charges. Read the full text of the Research Article at 10.1002/cphc.202200592.

Cluster Amplitudes and Their Interplay with Self-Consistency in Density Functional Methods.

Density functional theory (DFT) provides convenient electronic structure methods for the study of molecular systems and materials. Regular Kohn-Sham DFT calculations rely on unitary transformations to determine the ground-state electronic density, ground state energy, and related properties. However, for dissociation of molecular systems into open-shell fragments, due to the self-interaction error present in a large number of density functional approximations, the self-consistent procedure based on the this type of transformation gives rise to the well-known charge delocalization problem. To avoid this issue, we showed previously that the cluster operator of coupled-cluster theory can be utilized within the context of DFT to solve in an alternative and approximate fashion the ground-state self-consistent problem. This work further examines the application of the singles cluster operator to molecular ground state calculations. Two approximations are derived and explored: i) A linearized scheme of the quadratic equation used to determine the cluster amplitudes. ii) The effect of carrying the calculations in a non-self-consistent field fashion. These approaches are found to be capable of improving the energy and density of the system and are quite stable in either case. The theoretical framework discussed in this work could be used to describe, with an added flexibility, quantum systems that display challenging features and require expanded theoretical methods.

Slippery Paraelectric Transition-Metal Dichalcogenide Bilayers.

Traditional ferroelectrics undergo thermally induced phase transitions whereby their structural symmetry increases. The associated higher-symmetry structure is dubbed paraelectric. Ferroelectric transition-metal dichalcogenide bilayers have been recently shown to become paraelectric, but not much has been said of the atomistic configuration of such a phase. As discovered through numerical calculations that include molecular dynamics here, their paraelectricity can only be ascribed to a time average of ferroelectric phases with opposing intrinsic polarizations, whose switching requires macroscopically large areas to slip in unison.

Theoretical quantum model of two-dimensional propagating plexcitons.

When plasmonic excitations of metallic interfaces and nanostructures interact with electronic excitations in semiconductors, new states emerge that hybridize the characteristics of the uncoupled states. The engendered properties make these hybrid states appealing for a broad range of applications, ranging from photovoltaic devices to integrated circuitry for quantum devices. Here, through quantum modeling, the coupling of surface plasmon polaritons and mobile two-dimensional excitons such as those in atomically thin semiconductors is examined with emphasis on the case of strong coupling. Our model shows that at around the energy crossing of the dispersion relationships of the uncoupled species, they strongly interact and polariton states-propagating plexcitons-emerge. The temporal evolution of the system where surface plasmon polaritons are continuously injected into the system is simulated to gain initial insight on potential experimental realizations of these states. The results show a steady state that is dominated by the lower-energy polariton. The study theoretically further establishes the possible existence of propagating plexcitons in atomically thin semiconductors and provides important guidance for the experimental detection and characterization of such states for a wide range of optoelectronic technologies.

Thermal properties of single-layer MoS2-WS2 alloys enabled by machine-learned interatomic potentials.

Two-dimensional (2D) quantum materials are poised to transform conventional electronics for a wide spectrum of applications that will encompass chemical sciences. For the study of thermal transport in single-layer (1L) or multi-layer transition metal dichalcogenides (TMDs), this work explores the combination of density functional theory (DFT) and algorithmic training for the generation of a moment tensor potential (MTP) that models 1L-MoS2, 1L-WS2 and their alloys, and demonstrates a synergy of theoretical techniques that is anticipated to play an important role in the field. From a high-performance computing perspective, these yield very convenient inter-atomic (or inter-molecular in other contexts) potentials that are useful to predict the response of quantum materials to thermal perturbations, or other driving forces. We show that our trained MTP functions successfully describe vibrational properties of the systems, and their thermal conductivities. The trained potential displays consistent agreement with DFT calculations, as well as the Stillinger-Weber (SW) potential. We also find that the thermal conductivity of the 2D alloys is little affected by sulfur vacancies. This is a behavior that may aid the fine-tuning of material's thermal properties for heat management and energy storage and conversion applications.

Understanding the Origin of Enhanced Piezoelectric Response in PVDF Matrices with Embedded ZnO Nanoparticles, from Polarizable Molecular Dynamics Simulations.

The pervasive use of portable electronic devices, powered from rechargeable batteries, represents a significant portion of the electricity consumption in the world. A sustainable and alternative energy source for these devices would require unconventional power sources, such as harvesting kinetic/potential energy from mechanical vibrations, ultrasound waves, and biomechanical motion, to name a few. Piezoelectric materials transform mechanical deformation into electric fields or, conversely, external electric fields into mechanical motion. Therefore, accurate prediction of elastic and piezoelectric properties of materials, from the atomic structure and composition, is essential for studying and optimizing new piezogenerators. Here, we demonstrate the application of harmonic-covalent and reactive force fields (FF), Dreiding and ReaxFF, respectively, coupled to the polarizable charge equilibration (PQEq) model for predicting the elastic moduli and piezoelectric response of crystalline zinc oxide (ZnO) and polyvinylidene difluoride (PVDF). Furthermore, we parametrized the ReaxFF atomic interactions for Zn-F in order to characterize the interfacial effects in hybrid PVDF matrices with embedded ZnO nanoparticles (NPs). We capture the nonlinear piezoelectric behavior of the PVDF-ZnO system at different ZnO concentrations and the enhanced response that was recently observed experimentally, between 5 and 7 wt % ZnO concentrations. From our simulation results, we demonstrate that the origin of this enhancement is due to an increase in the total atomic stress distribution at the interface between the two materials. This result provides valuable insight into the design of new and improved piezoelectric nanogenerators and demonstrates the practical value of these first-principles based modeling methods in materials science.

Effect of surface oxidation on the electronic transport properties of phosphorene gas sensors: a computational study.

The potential for phosphorene-based devices has been compromised by the material's fast degradation under ambient conditions. Its tendency to fully oxidize under O2-rich and humid environments, leads to the loss of its appealing semiconducting properties. However, partially-oxidized phosphorene (po-phosphorene), has been demonstrated to remain stable over significantly longer periods of time, thereby enabling its use in sensing applications. Here, we present a computational study of po-phosphorene-based gas sensors, using the Density-Functional-based Tight Binding (DFTB) method. We show that DFTB accurately predicts the bandgap for the pristine material and po-phosphorene, the electronic transport properties of po-phosphorene at different surface oxygen concentrations, and the appropriate trends in Density-of-States (DOS) contributions caused by adsorbed gas molecules, to demonstrate its potential application in the development of gas sensors. Results are compared against the more traditional and expensive Density Functional Theory (DFT) method using generalized gradient approximation (GGA) exchange-correlation functionals, which significantly underestimates the material's bandgap.

Partially-oxidized phosphorene sensor for the detection of sub-nano molar concentrations of nitric oxide: a first-principles study.

The development of new techniques or instruments for detecting and accurately measuring biomarker concentrations in living organisms is essential for early diagnosis of diseases, and for tracking the effectiveness of treatments. In chronic diseases, such as asthma, precise phenotyping can help predict the response of patients to treatments and reduce the risk of complications. Fractional exhaled nitric oxide (FeNO) is a positive biomarker for eosinophilic asthma in humans, and it can be directly detected in the respiratory tract, at very low and volatile concentrations, which makes real-time measurement a challenge. This work describes the first-principles design and characterization of a molecular- and back-gated electronic field-effect transistor device for the detection and measurement of ultra-low FeNO concentrations (pM-nM) from a person' s exhaled breath, as a cost-efficient alternative to the slower and more expensive techniques based on off-line sputum characterization via mass spectrometry. The proposed device uses a partially oxidized phosphorene semiconducting channel material for FeNO detection, allowing nM L-1 concentration measurements of this analyte in an array configuration with an effective sensing surface area of 8.775 µm2, which results in a predicted limit of detection (LOD) of 19 nM L-1. In spite of the limited stability of phosphorene in oxygen-rich and humid environments, the proposed device would be practical for mobile applications with disposable sensors.