Enhanced Charge Separation in Single Atom Cobalt Based Graphitic Carbon Nitride: Time Domain Analysis.

In recent years, single atom catalysts have been at the forefront of energy conversion research, particularly in the field of catalysis. Carbon nitrides offer great potential as hosts for stabilizing metal atoms due to their unique electronic structure. We use nonadiabatic molecular dynamics to study photoexcitation dynamics in single atom cobalt based graphitic carbon nitride.

Charge Carrier Dynamics at the Interface of 2D Metal-Organic Frameworks and Hybrid Perovskites for Solar Energy Harvesting.

Interfacing perovskites with two-dimensional materials such as metal-organic frameworks (MOFs) for improved stability and electron or hole extraction has emerged as a promising path forward for the generation of highly efficient and stable solar cells. In this work, we examine the structural properties and excitation dynamics of two MOF-perovskite systems: UMCM309-a@MAPbI and ZrL3@MAPbI. We find that precise band alignment and electronegativity of the MOF-linkers are necessary to facilitate the capture of excited charge carriers.

Pyrovskite: A software package for the high-throughput construction, analysis, and featurization of two- and three-dimensional perovskite systems.

The increased computational and experimental interest in perovskite systems comprising novel phases and reduced dimensionality has greatly expanded the search space for this class of materials. In similar fields, unified frameworks exist for the procedural generation and subsequent analysis of these complex condensed matter systems. Given the relatively recent rise in popularity of these novel perovskite phases, such a framework is yet to be created.

Investigating the Increased CO Capture Performance of Amino Acid Functionalized Nanoporous Materials from First-Principles and Grand Canonical Monte Carlo Simulations.

Nanoporous materials such as metal-organic frameworks (MOFs) and covalent-organic frameworks (COFs) have been identified as key candidates for environmental remediation through catalytic reduction and sequestration of pollutants. Given the prevalence of CO as a target molecule for capture, MOFs and COFs have seen a long history of application in the field. More recently, functionalized nanoporous materials have been demonstrated to improve performance metrics associated with the capture of CO.

Computational Insights into Prostaglandin E Ligand Binding and Activation of G-Protein-Coupled Receptors.

G-protein coupled receptors (GPCRs) are eukaryotic integral membrane proteins that regulate signal transduction cascade pathways implicated in a variety of human diseases and are consequently of interest as drug targets. For this reason, it is of interest to investigate the way in which specific ligands bind and trigger conformational changes in the receptor during activation and how this in turn modulates intracellular signaling. In the present study, we investigate the way in which the ligand Prostaglandin E2 interacts with three GPCRs in the E-prostanoid family: EP1, EP2, and EP3.

Atomistic Description of the Impact of Spacer Selection on Two-Dimensional (2D) Perovskites: A Case Study of 2D Ruddlesden-Popper CsPbI Analogues.

Inorganic CsPbI perovskites have become desirable for use in photovoltaic devices due to their excellent optoelectronic properties and increased resilience to thermal degradation compared to organic-inorganic perovskites. An effective strategy for improving both the performance and the phase stability of CsPbI-based perovskites is through introducing a diverse set of spacing cations separating inorganic layers in their two-dimensional (2D) analogues. In this work, CsPbI-based 2D Ruddlesden-Popper perovskites were investigated using three aromatic spacers, 2-thiophenemethylamine (ThMA), 2-thiopheneformamidine (ThFA), and benzylammonium, fluorinated through substitution (pFBA).

Computational Investigations of Metal-Organic Frameworks as Sorbents for BTEX Removal.

Sequestration of aromatic volatile organic compounds (VOCs) via metal-organic frameworks (MOFs) as sorbents is a viable means of environmental preservation. In this investigation, we shed light on the key features associated with MOFs that govern the selective uptake of a subclass of VOCs containing benzene, toluene, ethylbenzene, and xylenes (BTEX). We investigate, through a multistep computational framework including electronic structure and classical molecular dynamics simulations, the energetic and dynamical properties associated with BTEX capture in three MOFs: HKUST-1, ZIF-8, and MIL-53.

Probing Strain-Induced Effects on Performance of Low-Dimensional Hybrid Perovskites for Solar Energy Harvesting.

The application of strain to photovoltaics (PVs), thermoelectrics (TEs), and semiconductors often has substantial impacts on the fundamental properties governing the efficiency of these materials. In this work, we investigate two stable phases of hybrid organic-inorganic two-dimensional (2D) perovskites (2DPKs) and their response to the application of tensile and compressive strain of up to 5%. These 2D MAPbI analogues are known to exhibit strongly anisotropic properties and have been put forward as excellent candidates for application in mixed PV-TE devices.

Charge carrier nonadiabatic dynamics in non-metal doped graphitic carbon nitride.

Graphitic carbon nitride (GCN) has attracted significant attention due to its excellent performance in photocatalytic applications. Non-metal doping of GCN has been widely used to improve the efficiency of the material as a photocatalyst. Using a combination of time-domain density functional theory with nonadiabatic molecular dynamics, we study the charge carrier dynamics in oxygen and boron doped GCN systems.

Capture of Toxic Oxoanions from Water Using Metal-Organic Frameworks.

The effective capture of common water contaminants using metal-organic frameworks (MOFs) presents a remedy for current environmental concerns arising from the pollution of water sources. The crystalline porous nature of MOFs, their high internal surface area, and exceptional tunability make them suitable candidates for sequestration and removal of pollutants. However, the efficiency of capture depends largely on the nature of the interactions between the anions and the MOF.

Ultrafast Removal of Phosphate from Eutrophic Waters Using a Cerium-Based Metal-Organic Framework.

Phosphate removal has become a critical need to mitigate the negative effect of water eutrophication, which is responsible for the overgrowth of toxic algal blooms and the significant ecological harm generated to aquatic ecosystems. However, some of the currently available adsorbents have low removal capacity and function optimally at specific pH ranges. Here, we present an example of a cerium-based metal-organic framework (MOF) as a high-capacity sorbent for phosphate removal from eutrophic waters.

Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters.

The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster.

Ab initio quantum dynamics of charge carriers in graphitic carbon nitride nanosheets.

Graphitic carbon nitride (g-CN), a metal-free and visible light responsive photocatalyst, has garnered much attention due to its wide range of applications. In order to elucidate the role of dimensionality on the properties of photo-generated charge carriers, we apply nonadiabatic (NA) molecular dynamics combined with time-domain density functional theory to investigate nonradiative relaxation of hot electrons and holes, and electron-hole recombination in monolayer and bulk g-CN. The nonradiative charge recombination occurs on a nanosecond timescale and is faster in bulk than the nanosheet, in agreement with the experiment.

Nonadiabatic Molecular Dynamics for Thousand Atom Systems: A Tight-Binding Approach toward PYXAID.

Excited state dynamics at the nanoscale requires treatment of systems involving hundreds and thousands of atoms. In the majority of cases, depending on the process under investigation, the electronic structure component of the calculation constitutes the computation bottleneck. We developed an efficient approach for simulating nonadiabatic molecular dynamics (NA-MD) of large systems in the framework of the self-consistent charge density functional tight binding (SCC-DFTB) method.

Decoherence Allows Model Reduction in Nonadiabatic Dynamics Simulations.

A nonadiabatic (NA) molecular dynamics (MD) simulation requires calculation of NA coupling matrix elements, the number of which scales as a square of the number of basis states. The basis size can be huge in studies of nanoscale materials, and calculation of the NA couplings can present a significant bottleneck. A quantum-classical approximation, NAMD overestimates coherence in the quantum, electronic subsystem, requiring decoherence correction.

Auger-mediated electron relaxation is robust to deep hole traps: time-domain ab initio study of CdSe quantum dots.

By slowing down electron-phonon relaxation in nanoscale materials, one can increase efficiencies of solar energy conversion via hot electron extraction, multiple exciton generation, and elimination of exciton trapping. The elusive phonon bottleneck is hard to achieve, in particular, due to Auger-type energy exchange between electrons and holes. The Auger channel can be suppressed by hole trapping.