Enhanced Charge Separation in Single Atom Cobalt Based Graphitic Carbon Nitride: Time Domain Ab Initio 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 ab initio nonadiabatic molecular dynamics to study photoexcitation dynamics in single atom cobalt based graphitic carbon nitride. The results elucidate the positive effect of the doped cobalt atom on the electronic structure of GCN. Cobalt doping produces filled midgap states that serve as oxidation centers, advantageous for various redox reactions. The presence of midgap states enables the harvesting of longer wavelength photons, thereby extending the absorption range of solar light. Although doping accelerates charge relaxation overall, charge recombination is significantly slower than charge separation, creating beneficial conditions for catalysis applications. The simulations reveal the detailed microscopic mechanism underlying the improved performance of the doped system due to atomic defects and demonstrate an effective charge separation strategy to construct highly efficient and stable photocatalytic two-dimensional materials.

Computational Insights into Prostaglandin E2 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. We examine information transfer pathways based on long-time scale molecular dynamics simulations using transfer entropy and betweenness centrality to measure the physical transfer of information among residues in the system. We monitor specific residues involved in binding to the ligand and investigate how the information transfer behavior of these residues changes upon ligand binding. Our results provide key insights that enable a deeper understanding of EP activation and signal transduction functioning pathways at the molecular level, as well as enabling us to make some predictions about the activation pathway for the EP1 receptor, for which little structural information is currently available. Our results should advance ongoing efforts in the development of potential therapeutics targeting these receptors.

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@MAPbI3 and ZrL3@MAPbI3. We find that precise band alignment and electronegativity of the MOF-linkers are necessary to facilitate the capture of excited charge carriers. Furthermore, we demonstrate that intraband relaxation of hot electrons to the MOF subsystem results in optically disallowed transitions across the band gap, suppressing radiative recombination. Furthermore, we elucidate the key mechanisms associated with improved structural stability afforded to the perovskites by the two-dimensional MOFs, highlighting the necessity of broad surface coverage and strong MOF-perovskite interaction.

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. In this work, we introduce Pyrovskite, an open source software package, to aid in both the high-throughput and fine-grained generation, simulation, and subsequent analysis of this expanded family of perovskite systems. Additionally, we introduce a new descriptor for octahedral distortions in systems, including, but not limited to, perovskites. This descriptor quantifies diagonal displacements of the B-site cation in a BX6 octahedral coordination environment, which has been shown to contribute to increased Rashba-Dresselhaus splitting in perovskite systems.

Investigating the Increased CO2 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 CO2 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 CO2. We employ a multiscale computational approach including ab initio density functional theory (DFT) calculations and classical grand canonical Monte Carlo (GCMC) simulations, to investigate the impact of amino acid (AA) functionalization in three such nanoporous materials. Our results demonstrate a nearly universal improvement of CO2 uptake metrics such as adsorption capacity, accessible surface area, and CO2/N2 selectivity for six AAs. In this work, we elucidate the key geometric and electronic properties associated with improving the CO2 capture performance of functionalized nanoporous materials.

Atomistic Description of the Impact of Spacer Selection on Two-Dimensional (2D) Perovskites: A Case Study of 2D Ruddlesden-Popper CsPbI3 Analogues.

Inorganic CsPbI3 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 CsPbI3-based perovskites is through introducing a diverse set of spacing cations separating inorganic layers in their two-dimensional (2D) analogues. In this work, CsPbI3-based 2D Ruddlesden-Popper perovskites were investigated using three aromatic spacers, 2-thiophenemethylamine (ThMA), 2-thiopheneformamidine (ThFA), and benzylammonium, fluorinated through para substitution (pFBA). Our findings highlight the importance of the local bonding environment between organic spacers and the PbI6 octahedra. Additionally, we demonstrated the importance of energetic alignment between electronic states on spacing cations and inorganic layers for optoelectronic applications. Furthermore, thermoelectric performance was investigated revealing a preference for p-type ThFA and n-type ThMA and pFBA configurations.

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 ab initio 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. Our work demonstrates the importance of considering both static and dynamical properties upon introduction of guest molecules in such computational investigations. We elucidate the key geometric factors associated with efficient capture of BTEX compounds and highlight possible postsynthetic modifications that can be used to produce next generation sorbents for BTEX capture.

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 MAPbI3 analogues are known to exhibit strongly anisotropic properties and have been put forward as excellent candidates for application in mixed PV-TE devices. Our results, stemming from ab initio density functional theory calculations and investigation of transport properties through the Boltzmann transport equations, further elucidate the key properties contributing to the success of these materials. In particular, both the M1 and M2 phases exhibit stable structures between -5 and 5% biaxial strains. The M2 phase exhibits an excellent 23.8% power conversion efficiency under the application of 5% tensile strain. Furthermore, we analyze the effects of spin-orbit coupling on the band structures of both phases, revealing great potential for spintronic applications with the M2 phase, demonstrating Rashba coefficients up to 3.67 eV Å.

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. The reported simulations provide a detailed time-domain mechanistic description of the charge separation and recombination processes that are of fundamental importance while evaluating the photovoltaic and photocatalytic performance of the material. The appearance of smaller energy gaps due to the presence of dopant states improves the visible light absorption range of the doped systems. At the same time, the nonradiative lifetimes are shortened in the doped systems as compared to the pristine GCN. In the case of boron doped at a carbon (B-C-GCN), the charge recombination time is very long as compared to the other two doped systems owing to the smaller electron-phonon coupling strength between the valence band maximum and the trap state. The results suggest B-C-GCN as the most suitable candidate among three doped systems studied in this work for applications in photocatalysis. This work sheds light into the influence of dopants on quantum dynamics processes that govern GCN performance and, thus, guides toward building high-performance devices in photocatalysis.

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. In this work, to elucidate the host-guest interactions involved in the capture of such pollutants, we explore three characteristically different MOFs: ZIF-8, iMOF-2c, and MOF-74. We demonstrate by ab initio electronic structure calculations the importance of exploiting qualitatively different binding modes for strong host-guest interactions available in the selected MOFs. Our simulations reveal the relative performance of neutral and cationic adsorbents while underscoring the importance of employing MOFs containing open metal sites for the efficient uptake of anions.

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. Specifically, a Ce(IV)-based UiO-66 analogue, Ce 1,4-benzenedicarboxylate (Ce-BDC), was selected due to its water stability, high surface area, microporous structure, and the high binding affinity of phosphate with its open metal sites. Mechanistic studies supported by density functional theory (DFT) calculations indicate the formation of a Ce-O-P bond through ion exchange between the terminal (nonbridging) hydroxyl groups at the missing linker sites and the phosphate adducts. Experimental results demonstrate that Ce-BDC is highly selective for phosphates over other common anions (Cl-, Br-, I-, NO3-, HCO3-, SO42-) and stable in a broad pH range of (2-12), covering the relevant range for the treatment of contaminants in aquatic systems. The sorbent shows a fast removal rate, capturing significant amounts of phosphate within 4 min with a maximum adsorption capacity of 179 mg·g-1, outperforming other porous materials. These results show a remarkable adsorption capacity and fast kinetics compared with the current state-of-the-art crystalline porous materials. This study may advance the design of new microporous materials with high adsorption capabilities, good stability, and make a significant contribution to the development of future generation technology to mitigate the negative effects of water eutrophication.

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. We observe a decrease in the CM enhancement factor with an increase in the atomic number of the halogen for para-substitutions. For meta-substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with the increasing solvent dielectric constant. The correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal and the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.

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

Graphitic carbon nitride (g-C3N4), 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-C3N4. The nonradiative charge recombination occurs on a nanosecond timescale and is faster in bulk than the nanosheet, in agreement with the experiment. The difference arises due to the smaller energy gap and participation of additional vibrations in the bulk system. The long carrier lifetimes are favored by small NA coupling and rapid phonon-induced loss of quantum coherence between the excited and ground electronic states. Decoherence is fast because g-C3N4 is soft and undergoes large scale vibrations. The NA coupling is small since electrons and holes are localized on different atoms, and the electron-hole overlap is relatively small. Phonon-driven relaxation of hot electrons and holes takes 100-200 fs and is slightly slower at higher initial energies due to participation of fewer vibrational modes. This feature of two-dimensional g-C3N4 contrasts traditional three-dimensional semiconductors, which exhibit faster relaxation at higher energies due to larger density of states, and can be used to extract hot carriers to perform useful functions. The ab initio quantum dynamics simulations present a comprehensive picture of the photo-induced charge carrier dynamics in g-C3N4, guiding design of photovoltaic and photocatalytic devices.

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. SCC-DFTB is combined with the fewest switches surface hopping (FSSH) and decoherence induced surface hopping (DISH) techniques for NA-MD. The approach is implemented within the Python extension for the ab initio dynamics (PYXAID) simulation package, which is an open source NA-MD program designed to handle nanoscale materials. The accuracy of the developed approach is tested with ab initio DFT and experimental data, by considering intraband electron and hole relaxation, and nonradiative electron-hole recombination in a CdSe quantum dot and the (10,5) semiconducting carbon nanotube. The technique is capable of treating accurately and efficiently excitation dynamics in large, realistic nanoscale materials, employing modest computational resources.

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. Generally, decoherence times decrease with increasing energy separation between pairs of states forming coherent superpositions. Since rapid decoherence stops quantum dynamics, one expects that decoherence-corrected NAMD can eliminate the need for calculation of NA couplings between energetically distant states, notably reducing the computational cost. Considering several types of dynamics in a semiconductor quantum dot, we demonstrate that indeed, decoherence allows one to reduce the number of needed NA coupling matrix elements. If the energy levels are spaced closer than 0.1 eV, one obtains good results while including only three nearest-neighbor couplings, and in some cases even with just the first nearest-neighbor coupling scheme. If the energy levels are spaced by about 0.4 eV, the nearest-neighbor model fails, while three or more nearest-neighbor schemes also provide good results. In comparison, the results of NAMD simulation without decoherence vary continuously with changes in the number of NA couplings. Thus, decoherence effects induced by coupling to a quantum-mechanical environment not only provide the physical mechanism for NAMD trajectory branding and improve the accuracy of NAMD simulations, but also afford significant computational savings.

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. Using time-domain ab initio simulation, we show that deep hole traps cannot fully eliminate the Auger channel. The simulations show that the hole-mediated electron relaxation is slowed down only by about 30%, which is in agreement with the recent experiments. The Auger energy exchange and hole relaxation to the trap state occur on similar time scales. Hole trapping is slow, because holes themselves experience a weak bottleneck effect. The study establishes the fundamental mechanisms of the electron and hole relaxation processes with and without hole traps. It shows that more sophisticated hole trapping strategies, for example, involving shell layers, are required in order to achieve the phonon bottleneck and to reduce electronic energy losses.