Transition Density Research Articles

Computational modeling of oligothiophenes‐based donor molecules to boost optoelectronic attributes of organic solar cells

AbstractThe computational modeling of seven oligothiophene‐based donor molecules (TZ1–TZ7) designed by acceptor modification at the terminal position of the literature molecule (TZR) were discussed for organic solar cells (OSCs). DFT simulations using B3LYP/def2svp levels were performed to study the optoelectronic, and PV properties of TZ1–TZ7. A range of essential aspects for efficient small donor molecules like open circuit voltages (VOC), excitation energy (Ex), dipole moment (μ), density of state (DOS), absorption maxima (λmax), transition density matrix (TDM), binding energy (Eb), and frontier molecular orbitals (FMOs) of TZ1–TZ7 and TZR have also been investigated. DOS and FMOs analysis revealed a reduced energy gap (Eg) and effective charge transfer (CT) in the TZ1–TZ7 molecules. The absorption spectra were examined using TD‐DFT. Due to smaller Eg, Eb, Ex, and higher λmax, μ, the TZ1–TZ7 molecules exhibit remarkable optoelectronic properties. The computed VOC (0.969–1.189) and fill factor (0.886–0.897) for TZ1–TZ7 lead to improved power conversion efficiency (PCE) ranging from 14.05% to 17.60%. All compounds are strongly recommended for fabricating efficient OSCs with excellent PV properties. The current work is a step towards environmentally friendly organic PV and will pave the way for future structural engineering research for the efficient material design of OSCs.

Improved the optical nonlinearity of carbazole based chromophores via molecular engineering: A DFT approach

The present investigation was based on designing of carbazole based derivatives (DTCFD1–DTCFD8) having D1-π-D2-π-A architecture from DTCFR, upon substituting acceptor motifs for nonlinear optical (NLO) materials. M06-2X/6-311G(d,p) level was accomplished to explore the optoelectronic behavior of designed compounds. The UV–Vis, density of states (DOS), natural bond orbitals (NBOs), transition density matrix (TDM) and frontier molecular orbitals (FMOs) analyses were executed to comprehend the nonlinear optical properties of above-mentioned compounds. The FMO analysis showed DTCFD7 as having the lowest energy gap at 3.734 eV among the derivatives, indicating its potential for efficient charge transfer. The overall decreasing order of band gaps was observed: DTCFR > DTCFD5 > DTCFD3 > DTCFD1 > DTCFD2 > DTCFD4 > DTCFD6 > DTCFD7. UV–Visible analysis exploited that DTCFD7 displayed distinctive absorption characteristics. In the gas phase, it exhibited a λmax of 494.927 nm, while in the dichloromethane it showed a significantly higher λmax of 516.515 nm, then all other derivatives. All the derivatives exhibited greater values of linear polarizability [〈α〉=1.633–1.786 × 10−22esu], first hyperpolarizability (βtot = 3.690–6.549 × 10−28esu) and second hyperpolarizability (γtot = 4.825–7.229 × 10−33esu) as compared to the reference molecule. Furthermore, NLO analysis revealed that the highest βtot (6.549 × 10−28esu) and γtot (7.229 × 10−33esu) was exhibited by DTCFD7 and DTCFD1, respectively, then other derivatives. Moreover, a comparative study with standard urea and para-nitroaniline (p-NA), exhibited effective NLO properties in current study compounds. In light of the comprehensive findings, this study concludes that the designed compounds may be considered as effective NLO materials.

Tailoring the donor moieties in TPA‐based organic dyes for efficient photovoltaic, optical and nonlinear optical response properties

AbstractThe current study reports tailoring the electronic donor structures of organic dyes to modify their optical and nonlinear optical (NLO) response properties. Five (5) tri‐phenyl amine (TPA) based Donor‐π‐Acceptor (D‐π‐A) organic dyes with the codes ICAA1, ICAA2, ICAA3, ICAA4, and ICAA5 were designed and investigated for their optical and NLO properties using quantum chemical methods. Optical and NLO properties of these dyes were studied by CAM‐B3LYP method and 6‐311G* basis set. The focus has been on the impact of adding secondary donors and shifting their substitutions at ortho (o), meta (m) and para (p) positions. Among all designed compounds, ICAA4 showed the highest amplitude of average third‐order NLO polarizability <γ>, which is calculated to be 1316 × 10−36 esu. Time‐dependent Density Functional Theory (TD‐DFT) method was used to determine how a change in the position of the donor affected the excitation energy (Eg) and NLO response properties. The findings showed that changing the position of the secondary donor results in a red shift among absorption spectra as well as the increase in their NLO responses. Complete process of intramolecular charge transfer (ICT) has been investigated in terms of different optical parameters such as frontier molecular orbitals (FMOs), molecular electrostatic potentials (MEPs), transition density matrix (TDMs), density of states (DOS), electron density difference (EDD), and natural bond orbital (NBO) analysis. Our calculations for study of ICT process indicate that p‐position of methoxy group performs better among all other positions and even it has better NLO response properties than the compound with three collective methoxy groups. The calculated Voc values of all designed molecules range from 1.09 to 1.30, all of them are positive while their ΔGinject is found to be in the range of −0.87 to −1.79 eV indicating their decent potential for photovoltaic applications. The studied optical, NLO and photovoltaic parameters illustrated that ICAA1 to ICAA5 are appropriate molecules not only for NLO applications but also for efficient photovoltaic purposes.

5‐Bromosalicylaldehyde: Theoretical, Experimental and Spectroscopic (FT‐IR, Raman, H1 and C13‐NMR, UV‐Vis) Studies and Their Photovoltaic Parameters

AbstractThis study aims to identify a 5‐bromosalicylaldehyde (5BSA) and assess its performance for application in organic solar cells. In the current work, the 5BSA was investigated using various techniques such as FT‐IR, Raman, NMR, and UV‐Vis spectroscopy to characterize the title molecule. The possible conformers of the 5BSA were studied using the MMFF methodology in Spartan software. The geometry optimization of modifications for each conformation was computed using the DFT approach for the B3LYP/6‐311++G(d,p) functional. The energy and dipole moment of most stable form were determined −1879057.42 kcal/mol and 1.455 Debye, respectively. The FT‐IR and Raman vibrational frequencies, the H1 and C13 NMR chemical shift values (in vacuum and in DMSO‐d6), the UV spectrum calculations (both in vacuum and in the solvent ethanol), the HOMO‐LUMO energy, and the map of MEP. Meanwhile, by considering the properties of organic photovoltaic cells, the open‐circuit voltage (VOC), hole reorganization energy (λh) and electron reorganization energy (λe), light‐harvesting efficiency (LHE), total reorganization energy (λtotal), the short‐circuit current density (Jsc), the driving force (ΔGinject), binding energy (Eb) were also computed for the title compound. In addition, transition density matrix (TDM) and density of states (DOS) analyses were conducted for the 5BSA molecule.

Preparation and characterizations of glasses in the TeO2–Ga2O3–M2O (M═Li, Na, K) systems

AbstractGlasses in the TeO2–Ga2O3–M2O (M═Li, Na, or K) systems were synthesized by a melt‐quenching technique. The glass forming areas were delimited for each system. Systematic analyses were performed on two series of samples—the first one with a constant TeO2/Ga2O3 ratio of 85/15, that is, [(TeO2)0.85(Ga2O3)0.15]100−x[M2O]x with 0 ≤ x ≤ 25 (with a step of 5 mol%), the second one with a constant alkaline oxide concentration of 10 mol%, that is, [TeO2]90‐y[Ga2O3]y[M2O]10 with 5 ≤ y ≤ 15 (with step of 2.5 mol%). The values of the glass transition temperature, density, and optical transmission parameters (the positions of short‐ and long‐wavelength absorption edge and the maximum transmittance value) were determined. The changes in these parameters were studied for varying glass compositions. In addition, the values of refractive index were measured at various wavelengths across the whole transparency region reaching from the visible up to the mid‐infrared range.

Demographic inference for spatially heterogeneous populations using long shared haplotypes

We introduce a modified spatial Λ-Fleming–Viot process to model the ancestry of individuals in a population occupying a continuous spatial habitat divided into two areas by a sharp discontinuity of the dispersal rate and effective population density. We derive an analytical formula for the expected number of shared haplotype segments between two individuals depending on their sampling locations. This formula involves the transition density of a skew diffusion which appears as a scaling limit of the ancestral lineages of individuals in this model. We then show that this formula can be used to infer the dispersal parameters and the effective population density of both regions, using a composite likelihood approach, and we demonstrate the efficiency of this method on a range of simulated data sets.

Synthesis of a new hydrazone-based schiff base: Spectroscopy, single crystal, DNA binding and theoretical studies

A new thiosemicarbazide-based Schiff base (TSDHB) was synthesized from thiosemicarbazide and 2,3-dihydroxybenzaldehyde. The prepared thiosemicarbazone was characterized by elemental (CHN), FT-IR, 1H and 13C NMR techniques. Furthermore, the molecular structure was probed using the single-crystal X-ray diffraction (SC-XRD) technique, which confirmed the enol tautomeric form with two independent molecules in asymmetric unit. The dissimilarity between the molecular units was determined by molecular overlay plots. The various intermolecular interactions and solid-state assembly stabilization were explored by Hirshfeld surface analysis. Void analysis was executed to examine the mechanical stability of crystalline units. The bioactivity of thiosemicarbazone was probed with the help of its binding capacity with salmon sperm DNA (SS-DNA) by means of the absorption interaction method. Accompanied by biological activity, optoelectronic properties such as nonlinear optical properties of yielded crystal were also explored through the DFT approach at M06/6–311 G (d,p). For this, various kinds of investigations such as frontier molecular orbital (FMO), UV–Vis, global reactivity parameters (GRPs), transition density matrix (TDM), density of states (DOS), natural population analysis (NPA), and natural bond orbital analysis (NBO) were executed at M06 functional. A good agreement was examined between XRD and DFT findings of molecular geometric parameters. Notably, in comparison with urea, TSDHB demonstrated enhanced nonlinear optical properties (linear polarizability=4.766 × 10−23esu and third-order hyperpolarizability=5.939 × 10−35esu). These findings position TSDHB as a promising candidate for DNA binding as well as for photonic materials due to its unique molecular characteristics and enhanced nonlinear optical behavior.

The influence of selenophene π-linker on photovoltaic properties of pyrrole-4,6(5-H)-dione-based chromophores: A quantum chemical study

A series of 4-H-selenopheno[3,4-c]pyrrole-4,6(5-H)-dione based chromophores (DMSD1-DMSD7) was designed via the introduction of selenophene units (n = 2–7) in the π–spacer of reference compound (DMSR) owing to growing demand of non-fullerene based organic solar cells. The influence of selenophene π–spacer on photovoltaic properties of entitled molecules was explored by utilizing CAM-B3LYP/6-311G (d,p) functional. All the designed compounds were found with lesser values of energy gaps (4.342–3.904 eV) as compared to DMSR (4.764 eV). Similarly, their absorption values were found in the visible region (523.560–533.403 nm) in dichloromethane solvent. Moreover, the entitled chromophores exhibited lower binding energies (1.895–1.566 eV) with higher open circuit voltage values which supported their excellent charge transference properties. The unique properties like least value of bandgap (3.904 eV) with greater charge transfer phenomena were examined for DMSD7 due to the presence of most elongated chain of selenophene-based π–spacer. The density of state and transition density matrix maps illustration further confirmed the efficient charge transfer in DMSD7. Overall, these findings disclosed that by utilizing selenophene π–spacer, photovoltaic properties of organic materials can be efficiently improved.

Investigating the impact of end-capped acceptor alterations to dimethyl fluorene-based hole transporting material for perovskite solar cells

Hole-transporting materials (HTMs) could boost the proficiency of third generation-perovskite solar cells since they have ultrafast charge mobility that improves optoelectronic and photovoltaic attributes. Five new H-shaped molecules were sketched using thiophene bridged, end-capped acceptor alteration on a dimethyl fluorene core-based molecule. Planarity measurements, absorption spectra, frontier molecular orbitals (FMOs), excitation energy (Ex), density of states (DOS), molecular electrostatic potentials (MEPs), transition density matrix (TDM), exciton binding energy, interaction coefficient, hole-electron overlap, open circuit voltage, fill factor, and power conversion efficiency were analyzed via DFT/MPW1P9W1/6-31G (d,p) for evaluating performance of perovskite solar cells. All newly sketched molecules with an A-π-D-π-A skeleton exhibited outstanding optoelectronic properties, including broader absorbance (563–740 nm) in chlorobenzene, indicating better solution processing. Lower band gaps (2.08–2.72 eV) than reference (3.78 eV) indicated efficient electron density transfer. Increased open-circuit voltage (1.55–2.02 eV) along with lower reorganization energies of the electron (0.043249–0.122527 eV) and hole (0.108105–0.148322 eV) lead to effective charge transport capabilities. Higher dipole moments indicated suitable film fabrication. A higher fill factor (0.9166–0.9325) and power conversion efficiency (34.31–45.49 %) led to an improved performance. Concisely, all the newly sketched molecules showed redshifted absorbance, narrower band gaps, deeper HOMO energies, improved charge transfer, higher softness, and smaller hardness values when compared to ZR, which confirms their superiority as future dopant-free HTM for PSCs.

The Physical Mechanism of Linear and Nonlinear Optical Properties of Nanographene-Induced Chiral Inversion.

Based on density functional theory (DFT) and wave function analysis, the ultraviolet and visible spectrophotometry (UV-Vis) spectra and Raman spectra of 1-meso and 1-rac obtained by the chiral separation of chiral nanographenes are theoretically investigated. The electron excitation properties of 1-meso and 1-rac are studied by means of transition density matrix (TDM) and charge density difference (CDD) diagrams. The intermolecular interaction is discussed based on an independent gradient model based on Hirshfeld partition (IGMH). The interaction of 1-meso and 1-rac with the external environment is studied using the electrostatic potential (ESP), and the electron delocalization degree of 1-meso and 1-rac is studied based on the magnetically induced current under the external magnetic field. Through the chiral separation of 1-rac, two enantiomers, 1-(P, P) and 1-(M, M), were obtained. The electrical-magnetic interaction of the molecule is revealed by analyzing the electron circular dichroism (ECD) spectra of 1-meso, 1-(P, P) and 1-(M, M), the transition electric dipole moment (TEDM) and the transition magnetic dipole moment (TMDM). It is found that 1-(P, P) and 1-(M, M) have opposite chiral properties due to the inversion of the structure.

Comparing the performance of machine learning methods in estimating the shear wave transit time in one of the reservoirs in southwest of Iran.

Shear wave transit time is a crucial parameter in petroleum engineering and geomechanical modeling with significant implications for reservoir performance and rock behavior prediction. Without accurate shear wave velocity information, geomechanical models are unable to fully characterize reservoir rock behavior, impacting operations such as hydraulic fracturing, production planning, and well stimulation. While traditional direct measurement methods are accurate but resource-intensive, indirect methods utilizing seismic and petrophysical data, as well as artificial intelligence algorithms, offer viable alternatives for shear wave velocity estimation. Machine learning algorithms have been proposed to predict shear wave velocity. However, until now, a comprehensive comparison has not been made on the common methods of machine learning that had an acceptable performance in previous researches. This research focuses on the prediction of shear wave transit time using prevalent machine learning techniques, along with a comparative analysis of these methods. To predict this parameter, various input features have been employed: compressional wave transit time, density, porosity, depth, Caliper log, and Gamma-ray log. Among the employed methods, the random forest approach demonstrated the most favorable performance, yielding R-squared and RMSE values of 0.9495 and 9.4567, respectively. Furthermore, the artificial neural network, LSBoost, Bayesian, multivariate regression, and support vector machine techniques achieved R-squared values of 0.878, 0.8583, 0.8471, 0.847 and 0.7975, RMSE values of 22.4068, 27.8158, 28.0138, 28.0240 and 37.5822, respectively. Estimation analysis confirmed the statistical reliability of the Random Forest model. The formulated strategies offer a promising framework applicable to shear wave velocity estimation in carbonate reservoirs.

Probing Activation and Conformational Dynamics of the Vesicle-Reconstituted β2 Adrenergic Receptor at the Single-Molecule Level.

G-protein-coupled receptors (GPCRs) are structurally flexible membrane proteins that mediate a host of physiological responses to extracellular ligands like hormones and neurotransmitters. Fine features of their dynamic structural behavior are hypothesized to encode the functional plasticity seen in GPCR activity, where ligands with different efficacies can direct the same receptor toward different signaling phenotypes. Although the number of GPCR crystal structures is increasing, the receptors are characterized by complex and poorly understood conformational landscapes. Therefore, we employed a fluorescence microscopy assay to monitor conformational dynamics of single β2 adrenergic receptors (β2ARs). To increase the biological relevance of our findings, we decided not to reconstitute the receptor in detergent micelles but rather lipid membranes as proteoliposomes. The conformational dynamics were monitored by changes in the intensity of an environmentally sensitive boron-dipyrromethene (BODIPY 493/503) fluorophore conjugated to an endogenous cysteine (located at the cytoplasmic end of the sixth transmembrane helix of the receptor). Using total internal reflection fluorescence microscopy (TIRFM) and a single small unilamellar liposome assay that we previously developed, we followed the real-time dynamic properties of hundreds of single β2ARs reconstituted in a native-like environment─lipid membranes. Our results showed that β2AR-BODIPY fluctuates between several states of different intensity on a time scale of seconds, compared to BODIPY-lipid conjugates that show almost entirely stable fluorescence emission in the absence and presence of the full agonist BI-167107. Agonist stimulation changes the β2AR dynamics, increasing the population of states with higher intensities and prolonging their durations, consistent with bulk experiments. The transition density plot demonstrates that β2AR-BODIPY, in the absence of the full agonist, interconverts between states of low and moderate intensity, while the full agonist renders transitions between moderate and high-intensity states more probable. This redistribution is consistent with a mechanism of conformational selection and is a promising first step toward characterizing the conformational dynamics of GPCRs embedded in a lipid bilayer.

Optical properties and exciton transfer between N-heterocyclic carbene iridium(III) complexes for blue light-emitting diode applications from first principles.

N-heterocyclic carbene (NHC) iridium(III) complexes are considered as promising candidates for blue emitters in organic light-emitting diodes. They can play the roles of the emitter as well as of electron and hole transporters in the same emission layer. We investigate optical transitions in such complexes with account of geometry and electronic structure changes upon excitation or charging and exciton transfer between the complexes from first principles. It is shown that excitation of NHC iridium complexes is accompanied by a large reorganization energy ∼0.7eV and a significant loss in the oscillator strength, which should lead to low exciton diffusion. Calculations with account of spin-orbit coupling reveal a small singlet-triplet splitting ∼0.1eV, whereas the oscillator strength for triplet excitations is found to be an order of magnitude smaller than for the singlet ones. The contributions of the Förster and Dexter mechanisms are analyzed via the explicit integration of transition densities. It is shown that for typical distances between emitter complexes in the emission layer, the contribution of the Dexter mechanism should be negligible compared to the Förster mechanism. At the same time, the ideal dipole approximation, although giving the correct order of the exciton coupling, fails to reproduce the result taking into account spatial distribution of the transition density. For charged NHC complexes, we find a number of optical transitions close to the emission peak of the blue emitter with high exciton transfer rates that can be responsible for exciton-polaron quenching. The nature of these transitions is analyzed.

Deep-LASI, single-molecule data analysis software

By avoiding ensemble averaging, single-molecule methods provide novel means of extracting mechanistic insights into function of material and molecules at the nanoscale. However, one of the big limitations is the vast amount of data required for analyzing and extracting the desired information, which is time-consuming and user dependent. Here, we introduce Deep-LASI, a software suite for the manual and automatic analysis of single-molecule traces, interactions, and the underlying kinetics. The software can handle data from one-, two- and three-color fluorescence data, and was particularly designed for the analysis of two- and three-color single-molecule fluorescence resonance energy transfer experiments. The functionalities of the software include: the registration of multiple-channels, trace sorting and categorization, determination of the photobleaching steps, calculation of fluorescence resonance energy transfer correction factors, and kinetic analyses based on hidden Markov modeling or deep neural networks. After a kinetic analysis, the ensuing transition density plots are generated, which can be used for further quantification of the kinetic parameters of the system. Each step in the workflow can be performed manually or with the support of machine learning algorithms. Upon reading in the initial data set, it is also possible to perform the remaining analysis steps automatically without additional supervision. Hence, the time dedicated to the analysis of single-molecule experiments can be reduced from days/weeks to minutes. After a thorough description of the functionalities of the software, we also demonstrate the capabilities of the software via the analysis of a previously published dynamic three-color DNA origami structure fluctuating between three states. With the drastic time reduction in data analysis, new types of experiments become realistically possible that complement our currently available palette of methodologies for investigating the nanoworld.

Extending the glass formation of alkali tellurites

The physical properties of low alkali content tellurite glasses of composition xM2O.(1−x)TeO2 (0≤x≤0·35) have been previously collected in this laboratory. The twin-roller rapid quenching technique (cooling rate>105°C/s), used within a nitrogen environment, successfully and significantly extended the glass-forming range in the lithium and sodium tellurite systems. The upper range for modification has been extended from x=0·35 to 0·80 and up to x=0·625 for the lithium and sodium systems, respectively. In the K, Rb and Cs tellurites, the glass forming ranges were not increased. Glass transition temperature (Tg), crystallisation temperature (Tx), density, molar volume, packing fraction, ionic conductivity and Raman spectra were obtained for these glasses. These results showed structural changes as a function of composition and carbonate retention in the glasses as the amount of alkali modifier increased above x=0·5.

Physical insight into optical spectroscopy of chiral covalent organic pillars as molecular nanotubes

In this paper, we theoretically investigate chiral covalent organic pillars synthesized by connecting rim-desymmetrized macrocycle, stimulated by recent experimental synthesis [Nat. Synth. 2023, 2, 395–402]. Transition densities reveal physical mechanism of spectral intensity in one-photon absorption (OPA) and two-photon absorption (TPA), and solvent effect strongly influence the spectral profile and intensity in TPA, but little influence the spectrum in OPA. The intra-unit and inter-unit charge transfer are visualized in five phenylenediamine linkers. The chirality of covalent organic pillars is revealed by electronic circular dichroism (ECD) spectroscopy, and interpreted by the visualized transition electric and magnetic dipole moments. Molecular vibrational information is demonstrated by normal and resonance Raman spectra and vibrational modes. The visualization of static and dynamic (hyper) polarization can reveal the physical mechanisms of polarization dependent normal and resonance Raman scattering. Our results provide deeper understanding on the physical mechanism of chiral covalent organic pillars as molecular nanotubes.

Visible Light Induced Exciton Dynamics and trans-to-cis Isomerization in Azobenzene Aggregates: Insights from Surface Hopping/Semiempirical Configuration Interaction Molecular Dynamics Simulations.

Assemblies of photochromic molecules feature exciton states, which govern photochemical and photophysical processes in multichromophoric systems. Understanding the photoinduced dynamics of the assemblies requires nonadiabatic treatment involving multiple exciton states and numerous nuclear degrees of freedom, thus posing a challenge for simulations. In this work, we address this challenge for aggregates of azobenzene, a prototypical molecular switch, performing on-the-fly surface hopping calculations combined with semiempirical configuration interaction electronic structure and augmented with transition density matrix analysis to characterize exciton evolution. Specifically, we consider excitation of azobenzene tetramers in the nπ* absorption band located in the visible (blue) part of the electromagnetic spectrum, thus extending our recent work on dynamics after ππ* excitation corresponding to the ultraviolet region [Titov, J. Phys. Chem. C2023, 127, 13678-13688]. We find that the nπ* excitons, which are initially strongly localized by ground-state conformational disorder, undergo further (very strong) localization during short-time photodynamics. This excited-state localization process is extremely ultrafast, occurring within the first 10 fs of photodynamics. We observe virtually no exciton transfer of the localized excitons in the nπ* manifold. However, the transfer may occur via secondary pathways involving ππ* states or the ground state. Moreover, we find that the nπ* quantum yields of the trans-to-cis isomerization are reduced in the aggregated state.

Novel cyano functional small molecule photosensitizers with amplified electron injection and photovoltaic attributes: molecular modelling towards efficient dye‐sensitized solar cells

AbstractBACKGROUNDThe exploration of novel photosensitizers with reverberant optoelectronic features for dye‐sensitized solar cells (DSSCs) is a frontline area of research. In this respect, attempts have been made to design a series of novel organic dyes (JFK‐1–JFK‐10) with D‐π‐A framework by π‐spacer modification strategy. The suitability of developed sensitizers for DSSCs applications is confirmed by executing natural bond orbital (NBO) analysis, transition density matrix (TDM) analysis, frontier molecular orbital (FMO) analysis, density of state (DOS) analysis, binding energy (Eb), electron regeneration energy (ΔGreg), free energy of injection (ΔGinject), electronic coupling constant (VRP), and intramolecular charge transfer (ICT) parameters qCT (e‐), DCT (Å), H index (Å), ∆(Å), t index (Å), μCT (D).RESULTSThe calculated results of these analyses show that replacing the thiophene (B0) π‐spacer with extended conjugated thiazole and thiophene as a π‐spacer (B1‐B10) results in significantly lowered FMO energy levels, broader λmax values, and ICT parameters respectively. All the proposed dyes could be used as excellent sensitizers for DSSCs; the B9 spacer in JFK‐9 makes JFK‐9 a highly efficient candidate for the high‐efficiency of DSSCs due to promising photovoltaic characteristics, like the reduced Egap (4.386 eV), longer λmax(427.989 nm), longer excited state lifetimes (1.483 ns), a lower ΔGreg (1.807 eV), a greater dipole moment of (9.475 D), and large qCT (0.546), LHE (0.981), and eVOC (1.729 eV).CONCLUSIONThe fabricated dyes’ (F1‐F9) photoelectronic and chemical transfer parameters near the titania‐electrolyte interface (dyes@TiO2) proved have better accumulation and recombination of dyes@TiO2 model. The adsorption energies calculated of all compounds provide a deep insight into adsorption and charge transfer to a semiconductor TiO2 conduction band. Hence, these modeled dyes (JFK‐1‐JFK‐10) could be used as efficient DSSCs and open new avenues for researchers to synthesize high‐performance DSSCs. © 2024 Society of Chemical Industry (SCI).

Global Investigations of Seawater Intrusion (SWI) in Coastal Groundwaters in the Last Two Decades (2000–2020): A Bibliometric Analysis

Seawater intrusion represents the flow of seawater through coastal aquifers, but it also affects surface water bodies such as channels, canals, and wetlands. Transitional water volumes, variable density and salinity distributions, and heterogeneous hydraulic properties describe coastal aquifers which are present in complex environments. The relationships between water density and salinity, climatic variations, groundwater pumps, and sea level fluctuations provide complex hydrological conditions related to the distribution of dissolved salts. This review will focus on (i) systematic evaluation of global SWI areas assessed by different methodologies and author contributions, (ii) SWI identified areas across the world using publication results, and (iii) bibliometric analysis of SWI publications for evaluation of the current status in coastal zone management, including the research gaps that are published in the Journal of Hydrology (5.91%), Environmental Geology (3.41%), Hydrogeology Journal (3.20%), Science of the Total Environment (1.60%), Water Resources Research (1.50%), Arabian Journal of Geosciences (1.30%), Environmental Earth Sciences (1.20%), Advances in Water Resources (1.10%), Applied Geochemistry (1.10%), Water Resources Management (1.0%), and Hydrological Processes (0.8%), a collection representing 30.59% (94 articles) of the total peer-reviewed scientific products of the past two decades focusing on the use of the present status of SWI in coastal aquifers, estuaries, and lagoons.

Designing Thieno[3,4-c]pyrrole-4,6-dione Core-Based, A2-D-A1-D-A2-Type Acceptor Molecules for Promising Photovoltaic Parameters in Organic Photovoltaic Cells.

Nonfullerene-based organic solar cells can be utilized as favorable photovoltaic and optoelectronic devices due to their enhanced life span and efficiency. In this research, seven new molecules were designed to improve the working efficiency of organic solar cells by utilizing a terminal acceptor modification approach. The perceived A2-D-A1-D-A2 configuration-based molecules possess a lower band gap ranging from 1.95 to 2.21 eV compared to the pre-existing reference molecule (RW), which has a band gap of 2.23 eV. The modified molecules also exhibit higher λmax values ranging from 672 to 768 nm in the gaseous and 715-839 nm in solvent phases, respectively, as compared to the (RW) molecule, which has λmax values at 673 and 719 nm in gas and chloroform medium, respectively. The ground state geometries, molecular planarity parameter, and span of deviation from the plane were analyzed to study the planarity of all of the molecules. The natural transition orbitals, the density of state, molecular electrostatic potential, noncovalent interactions, frontier molecular orbitals, and transition density matrix analysis of all studied molecules were executed to validate the optoelectronic properties of these molecules. Improved charge mobilities and dipole moments were observed, as newly designed molecules possessed lower internal reorganization energies. The open circuit voltage (Voc) of W4, W5, W6, and W7 among newly designed molecules was improved as compared to the reference molecule. These results elaborate on the superiority of these novel-designed molecules over the pre-existing (RW) molecule as potential blocks for better organic solar cell applications.