Pseudohalide-Based Ionic Liquids: Advancing Crystallization Kinetics and Optoelectronic Properties in All-Inorganic Perovskite Solar Cells.

This study delves into the innovative approach of enhancing the efficiency and stability of all-inorganic perovskite solar cells (I-PSCs) through the strategic incorporation of thiocyanate (SCN-) ions via pseudohalide-based ionic liquid (IL) configurations. This straightforward methodology has exhibited captivating advancements in the kinetics of crystallization as well as the optoelectronic characteristics of the resulting perovskite films. These developments hold the promise of enhancing not only the quality and uniformity of the films but also aspects such as band alignment and the efficacy of charge transfer mechanisms. Calculation results corroborate that the incorporation of 1-butyl-3-methylimidazolium thiocyanate (BmimSCN) led to a significant redistribution of electron state density and enhanced electron-donating properties, indicating a substantial electron transfer between the perovskite material and the IL. Notably, the engineered devices demonstrate a remarkable efficiency surpassing 15%, a substantial enhancement attributed to the synergistic effects of the SCN- ion. Additionally, this approach offers inherent stability benefits, thereby addressing a significant challenge in I-PSC technology. This IL maintains >90% of the initial efficiency after 600 h, while the control device decreased to <20% of its initial value after only 100 h. 1-butyl-3-methylimidazolium iodide (BmimI) is also employed to further investigate the effects of SCN- ions on device performance.

Quality of life before and after total knee arthroplasty in clinical settings across Lahore, Pakistan.

Knee osteoarthritis is a common disabling condition that affects a larger number of populations aged above 40 years and this habitually required knee arthroplasty to reinstate leg function, to improve the pain as well as to improve stability. The main objective of this study was to determine the health-related quality of lifestyle before and after total knee arthroplasty. This study was a cross-sectional observational study conducted at Shaukat Khanum Memorial Cancer Hospital & Research Centre, Horizon Hospital and Mayo Hospital, Lahore-Pakistan. In this study, 100 subjects were selected who were scheduled for Total Knee Replacement (TKR) due to advanced stages of knee osteoarthritis. Informed consent was taken from all selected patients. Selected subjects meeting inclusion and exclusion criteria were enrolled for this study. Subjects with any red flag signs or systemic illness were excluded. A baseline measurement was taken by using visual-analog scale (VAS) for pain, the Short Form 36 (SF-36) for health-related quality of life and The Western Ontario and McMaster Universities Osteoarthritis Index (WOMAC) for disability. Measurements using these scales were repeated after 1, 3 and 6 months after knee arthroplasty. Analysis of variance (ANOVA) test was used to determine statistically significant changes in VAS, SF 36 and WOMAC Score across 06 months. A significant (p<0.05) improvement in health-related quality of life measured of two subscales of SF 36 (Physical Health Component and Mental Health Component) when before surgery readings were compared with that of after 06 months of surgery. Similarly, there was also significant (p<0.05) reduction in pain measured on VAS as well as reduced WOMAC score before and after 06 months of surgery. It could be concluded that TKA results in the improvementof the quality of life and reduced pain following total knee arthroplasty.

Early-stage recovery of lithium from spent batteries via CO2-assisted leaching optimized by response surface methodology.

Recycling lithium (Li) from spent lithium-ion batteries (LIBs) due to the depletion of natural resources and potential toxicity is becoming a progressively favourable measure to realize green sustainability. Presently, the prevalent recycling technique relying on pyrometallurgy lacks the capability to extract lithium. Meanwhile, conventional hydrometallurgical processes frequently employ robust acidic solutions like sulfuric acid and precipitation agents such as sodium carbonate. Unfortunately, this approach tends to result in the extraction of lithium at the end of a lengthy process chain, leading to associated losses and creating challenges in managing complex waste. This study addresses a cost-effective and environmentally friendly early-stage lithium recovery from the thermally conditioned black mass. In this sense, a thermally conditioned black mass is subjected to the carbonization process in a water solution to transform the water-insoluble Li phase into soluble lithium bicarbonate (LiHCO3) and carbonate (Li2CO3) facilitating its selective separation from other elements. Response surface methodology (RSM)-a statistical tool integrated with central composite design (CCD) is employed to optimize the parameters for Li recovery. Temperature, solid-liquid (S/L) ratio, leaching time and CO2 flow rate are considered as variable factors in modelling the optimum recycling process. A quadratic regression model is developed for Li recovery and based on ANOVA analysis, (S/L) ratio, temperature and time are identified as statistically significant factors. Experimental results demonstrate a maximum leaching efficiency of lithium with optimized parameter set, achieving a recovery rate of 97.18% with a fit response of 93.54%.

Designing efficient materials for high-performance of non-fullerene organic solar cells through side-chain engineering on DBT-4F derivatives by non-fused-ring electron acceptors.

CONTEXT: For the advancement in fields of organic and perovskite solar cells, various techniques of structural alterations are being employed on previously reported chromophores. In this study, the end-capped engineering is carried out on DBT-4F (R) by modifying terminal acceptors to improve optoelectronic and photovoltaic attributes. Seven molecules (AD1-AD7) are modeled using different push-pull acceptors. DFT/B3LYP/6-31G along with its time-dependent approach (TD-DFT) are on a payroll to investigate ground state geometries, absorption maxima (λmax), energy gap (Eg), excitation energy (Ex), internal reorganization energy, light harvesting efficiency (LHE), dielectric constant, open circuit voltage (VOC), fill factor (FF), etc. of OSCs. AD1 displayed the lowest band gap (1.76 eV), highest λmax (876 nm), lowest Ex (1.41 eV), and lowest binding energy (0.21 eV). Among various calculated parameters, all of the sketched molecules demonstrated greater dielectric constant when compared to R. The highest dielectric constant was exhibited by AD3 (56.26). AD5 exhibited maximum LHE (0.9980). Lower reorganization energies demonstrated improved charge mobility. AD5 and AD7 (1.63 and 1.68 eV) have higher values of VOC than R (1.51 eV). All novel molecules having outperforming attributes will be better candidates to enhance the efficacy of OSCs for future use. METHODS: Precisely, a DFT and TD-DFT analysis on all of the proposed organic molecules were conducted, using the functional MPW1PW91 at 6-31G (d,p) basis set to examine their optoelectronic aspects, additionally the solvent-state computations were studied with a TD-SCF simulation. For all these simulations, Guassian 09 and GuassView 5.0 were employed. Moreover, the Origin 6.0, Multiwfn 3.8, and PyMOlyze 1.1 software were utilized for the visual depiction of the graphs of absorption, TDM, and DOS, respectively of the studied molecules. A number of crucial aspects such as FMOs, bandgaps, light-harvesting efficiency, electrostatic potential, dipole moment, ionization potential, open-circuit voltage, fill factor, binding energy, interaction coefficient, chemical hardness-softness, and electrophilicity index were also investigated for the studied molecules.

Tuning the optoelectronic properties of acridine-triphenylamine (ACR-TPA) based novel hole transporting material for high efficiency perovskite and organic solar cell.

In this research, five distinct small donor molecules (designated as ACR-TPA-X1, ACR-TPA-X2, ACR-TPA-X3, ACR-TPA-X4, ACR-TPA-X5) are constructed by replacing the methoxy groups on both sides of the model molecule (ACR-TPA-R) with thiophene bridged acceptor moieties. We have used the B3LYP/6-31G (d,p) model for our computational studies. Our model molecule's morphological alteration has resulted in a lowered Eg of 1.77-2.51 eV as compared to model (ACR-TPA-R=3.84 eV). ACR-TPA-X2 investigated the λmax at 776 nm. ACR-TPA-X4 was found to be most miscible with dichloromethane (DCM). The greatest VOC(1.21 eV) was observed in ACR-TPA-X1. Among all of the variants, ACR-TPA-X1 had the highest PCE (23.42%). It was found that ACR-TPA-X4 had the highest electron mobility (0.00370 eV) and ACR-TPA-X5 had the highest hole mobility (0.00324 eV) of all the materials examined. The findings prove the worth of the methods used, paving the way for the development of effective small donors for OSCs and HTMs for PSCs.

Methoxy triphenylamine hexaazatrinaphthylene based small molecules as donor material for photovoltaic applications.

Organic solar cells (OSCs) are capturing huge interest because of their numerous benefits, which include transparency, flexibility, and solution processability. In current project, five new donor molecules (J1-J5) were designed by employing the strategy of end capped alteration of the acceptor moieties on the two sides of the reference molecule. The Methoxy Triphenylamine hexaazatrinaphthylene (MeO-TPA-HATNA) have been used as a reference molecule in this study. DFT and TD-DFT methods employing B3LYP/6-31G (d, p) functional has been applied to perform different analysis. Geometrical, and opto-electronic features of all tailored chromophores were investigated, and comparison was made with the reference J. Among all tailored molecules, J5 shows highest λmax (862 nm) with the least band gap of 1.28 eV. TDM and DOS analysis revealed the high rate of charge transfer. Further, reorganization energy calculations are also executed to examine the charge transfer features of the designed molecules. The results shows that J5 among all these molecules has the highest rate of charge carrier (electron and hole) mobility with least RE values and this molecule can be used as a promising donor material for OSCs with remarkable charge transferring properties. Furthermore, the designed materials showed a suitable HOMO along with higher LUMO energy levels with respect to PC61BM molecule and coupling the PC61BM acceptor with investigated donor molecules gives highly increased Voc (0.66-0.76 V) than reference molecule (0.49 V) and also the power conversion efficiency (PCE) is elevated to 15.09%. The outcomes of current theoretical research have demonstrated that the end capped alteration of different acceptor groups is an excellent strategy to get OSCs with desirable photovoltaic performance. As, all the newly created molecules (J1-J5) have exhibited outstanding electronic and optical properties therefore, these can be expectedly prove excellent material for creating high efficiency future organic photovoltaic devices.

Designing Y-shaped two-dimensional (2D) polymer-based donor materials with addition of end group acceptors for organic and perovskite solar cells.

CONTEXT: For the advancement in fields of organic and perovskite solar cells, various techniques of structural alterations are being employed on previously reported chromophores. This way, molecules with all the properties desired for better performance of solar cells can be achieved. In this regard, theoretical modeling of chromophores has gained quite an interest due to its ability to save time, resources, and money. Herein, five new Y-shaped donor materials were theoretically engineered by adding electron-withdrawing acceptors on reported 2DP molecule. The results explored that, in comparison to 2DP, the produced molecules showed red shift in the absorption peaks, smaller bandgaps and binding energies, lower excitation potential, and greater dipole moment and were also highly reactive. When paired with PC61BM, proposed compounds exhibited higher estimated power conversion efficiencies and open-circuit voltage in contrast to 2DP. Individually, 2DP1 possessed the largest conductivity of electrons and the maximum mobility of holes, due to its computed lowest reorganization energies. The results illustrate the viability of the proposed procedure, opening doors for the manufacturing of required solar cells with enhanced photovoltaic properties. METHODS: Precisely, a DFT and TD-DFT analysis on 2DP and all of the proposed molecules was conducted, using the functional MPW1PW91 at 6-31G (d,p) basis set to examine their optoelectronic aspects; additionally, the solvent state computations were studied with a TD-SCF simulation. For all these simulations, Gaussian 09 and GaussView 5.0 were employed. Moreover, the Origin 6.0 software, Multiwfn 3.8 software, and PyMOlyze 1.1 software were utilized for the visual depiction of the graphs of absorption, TDM, and DOS, respectively, of the studied molecules. A number of crucial aspects such as FMOs, bandgaps, light-harvesting efficiency, electrostatic potential, dipole moment, ionization potential, open-circuit voltage, fill factor, binding energy, interaction coefficient, chemical hardness-softness, and electrophilicity index were also investigated for the studied molecules.

Quantum modeling of dimethoxyl-indaceno dithiophene based acceptors for the development of semiconducting acceptors with outstanding photovoltaic potential.

In the current DFT study, seven dimethoxyl-indaceno dithiophene based semiconducting acceptor molecules (ID1-ID7) are designed computationally by modifying the parent molecule (IDR). Here, based on a DFT exploration at a carefully selected level of theory, we have compiled a list of the optoelectronic properties of ID1-ID7 and IDR. In light of these results, all newly designed molecules, except ID5 have shown a bathochromic shift in their highest absorbance (λ max). ID1-ID4, ID6 and ID7 molecules have smaller band gap (E gap) and excitation energy (E x). IP of ID5 is the smallest and EA of ID1 is the largest among all others. Compared to the parent molecule, ID1-ID3 have increased electron mobility, with ID1 being the most improved in hole mobility. ID4 had the best light harvesting efficiency in this investigation, due to its strongest oscillator. The acceptor molecules' open-circuit voltages (V OC) were computed after being linked to the PTB7-Th donor molecule. Fill factor (FF) and normalized V OC of ID1-ID7 were calculated and compared to the parent molecule. Based on the outcomes of this study, the modified acceptors may be further scrutinised for empirical usage in the production of organic solar cells with enhanced photovoltaic capabilities.

Exploring the Electronic, Optical, and Charge Transfer Properties of A-D-A-Type IDTV-ThIC-Based Molecules To Enhance Photovoltaic Performance of Organic Solar Cells.

Improving the charge mobility and optoelectronic properties of indacenodithiophene-based small molecule acceptors is a key challenge to improving overall efficiency. In this current research, seven newly designed molecules (DT1-DT7) comprising the indacenodithiophene-based core are presented to tune energy levels, enhance charge mobility, and improve the photovoltaic performance of IDTV-ThIC molecules via density functional theory. All the molecules were designed by end-capped modification by substituting terminal acceptors of IDTV-ThIC with strong electron-withdrawing moieties. Among all the examined structures, DT1 has proved itself a superior molecule in multiple aspects, including higher λmax in chloroform (787 nm) and gaseous phase (727 nm), narrow band gap (2.16 eV), higher electron affinity (3.31 eV), least excitation energy (1.57 eV), and improved charge mobility due to low reorganization energy and higher excited state lifetime (2.37 ns) when compared to the reference (IDTV-ThIC) and other molecules. DT5 also showed remarkable improvement in different parameters, such as the lowest exciton binding energy (0.41 eV), leading to easier charge moveability. The improved open-circuit voltage of DT4 and DT5 makes them proficient molecules exhibiting the charge transfer phenomenon. The enlightened outcomes of these molecules can pave a new route to develop efficient organic solar cell devices using these molecules, especially DT1, DT4, and DT5.

Designing of anthracene-arylamine hole transporting materials for organic and perovskite solar cells.

This study focuses on the creation of 5 small donor molecules (A102W1-A102W5) by substituting the one-sided methoxy group of model (A102R) with different thiophene bridged acceptor moieties. B3LYP/6-31**G (d,p) model has been employed for computational analysis. The best miscibility was found for A102W3 in dichloromethane (DCM) solvent, where its λmax was also found to be at 753 nm, its Eg was found to be 1.55 eV as well as dipole moment in DCM was 21.47 D. The percentage of PCE among all the variants was greatest for A102W2 (25.31%). The electron reorganization energy shown by A102W4 was 0.00470 eV, whereas the hole reorganization energy investigated in A102W2 was 0.00586 eV representing their maximum electron and hole mobility respectively amongst all. Results validate the value of specified techniques, opening a new door to create efficient small donors for OSCs and HTMs for PSCs.

Designing of Thiophene [3, 2-b] Pyrrole Ring-Based NFAs for High-Performance Electron Transport Materials: A DFT Study.

Among the blended components of a photoactive layer in organic photovoltaic (OPV) cells, the acceptor is of high importance. This importance is attributed to its increased ability to withdraw electrons toward itself for their effective transport toward the respective electrode. In this research work, seven new non-fullerene acceptors were designed for their possible utilization in the OPVs. These molecules were designed through side-chain engineering of the PTBTP-4F molecule, with its fused pyrrole ring-based donor core and different strongly electron-withdrawing acceptors. To elucidate their effectiveness, the band gaps, absorption characteristics, chemical reactivity indices, and photovoltaic parameters of all of the architecture molecules were compared with the reference. Through various computational software, transition density matrices, graphs of absorption, and density of states were also plotted for these molecules. From some chemical reactivity indices and electron mobility values, it was proposed that our newly designed molecules could be better electron-transporting materials than the reference. Among all, TP1, due to its most stabilized frontier molecular orbitals, lowest band gap and excitation energies, highest absorption maxima in both the solvent and gas medium, least hardness, highest ionization potential, superior electron affinity, lowest electron reorganization energy, as well as highest rate constant of charge hopping, seemed to be the best molecule in terms of its electron-withdrawing abilities in the photoactive layer blend. In addition, in terms of all of the photovoltaic parameters, TP4-TP7 was perceived to be better suited in comparison to TPR. Thus, all our suggested molecules could act as superior acceptors to TPR.

Metallofullerenes as Robust Single-Atom Catalysts for Adsorption and Dissociation of Hydrogen Molecules: A Density Functional Study.

Hydrogen is currently considered as the best alternative for traditional fuels due to its sustainable and ecofriendly nature. Additionally, hydrogen dissociation is a critical step in almost all hydrogenation reactions, which is crucial in industrial chemical production. A cost-effective and efficient catalyst with favorable activity for this step is highly desirable. Herein, transition-metal-doped fullerene (TM@C60) complexes are designed and investigated as single-atom catalysts for the hydrogen splitting process. Interaction energy analysis (Eint) is also carried out to demonstrate the stability of designed TM@C60 metallofullerenes, which reveals that all the designed complexes have higher thermodynamic stability. Furthermore, among all the studied metallofullerenes, the best catalytic efficiency for hydrogen dissociation is seen for the Sc@C60 catalyst Ea = 0.13 eV followed by the V@C60 catalyst Ea = 0.19 eV. The hydrogen activation and dissociation processes over TM@C60 metallofullerenes is further elaborated by analyzing charge transfer via the natural bond orbital and electron density difference analyses. Additionally, quantum theory of atoms in molecule analysis is carried out to investigate the nature of interatomic interactions between hydrogen molecules and TMs@C60 metallofullerenes. Overall, results of the current study declare that the Sc@C60 catalyst can act as a low cost, highly efficient, and noble metal-free single-atom catalyst to efficiently catalyze hydrogen dissociation reaction.

Enhanced nonlinear optical response of alkalides based on stacked Janus all-cis-1,2,3,4,5,6-hexafluorocyclohexane.

Significant efforts are continuously exerted by the scientific community to explore new strategies to design materials with high nonlinear optical responses. An effective approach is to design alkalides based on Janus molecules. Herein, we present a new approach to remarkably boost the NLO response of alkalides by stacking the Janus molecules. Alkalides based on stacked Janus molecule, M-n-M' (where n = 2 & 3 while M and M' are Li/Na/K) are studied for structural, energetic, electrical, and nonlinear optical properties. The thermodynamic stability of the designed complexes is confirmed by the energetic stabilities, which range between -14.07 and -28.77 kcal/mol. The alkalide character of alkali metals-doped complexes is confirmed by the NBO charge transfer and HOMO(s) densities. The HOMO densities are located on the doped alkali metal atoms, indicating their alkalide character. The absorptions in UV-Vis and near IR region confirm the deep ultraviolet transparency of the designed complexes. The maximum first static and dynamic hyperpolarizabilities of 5.13 × 107 and 6.6 × 106 au (at 1339 nm) confirm their high NLO response, especially for K-2-M' complexes. The NLO response of alkalides based on stacked Janus molecules is 1-2 orders of magnitude higher than the alkalide based on Janus monomer. The high values of dc-Kerr and electric field-induced response e.g., max ∼107 and 108 au, respectively have been obtained. These findings suggest that our designed complexes envision a new insight into the rational design of stable high NLO performance materials.

Carbazole-based donor materials with enhanced photovoltaic parameters for organic solar cells and hole-transport materials for efficient perovskite solar cells.

Five carbazole-based donor molecules are designed by structural engineering of reference molecule PF. The molecules are devised by substitution of thiophene bridged end-capped acceptor groups namely (2-methylenemalononitrile) PF1, (methyl 2-cyanoacrylate) PF2, (3-methyl-5-methylene-2-thioxothiazolidin-4-one) PF3, (2-(3-methyl-5-methylene-4-oxothiazolidin-2- ylidene) malononitrile) PF4, and (4-(5-methylthiophen-2-yl) benzo[c] [1, 2, 5] thiadiazol) PF5. A DFT investigation was performed at the selected DFT functional MPW1PW91/6-31G (d,p) to investigate the optoelectronic properties of PF and all designed (PF1-PF2) molecules. Several important characteristics, i.e., band gap (Eg), transition density matrix analysis, dipole moment (µ), density of states analysis, reorganization energies, open circuit voltage (Voc), and fill factor, were investigated. The comparison of energy levels of reference molecule and designed molecules unveils the fact that these molecules are efficient hole transport materials to be used in perovskite solar cells (PSCs). All the newly drafted molecules (PF1-PF5) show higher λmax values in solvent (Chlorobenzene) ranging from 529 to 614 nm than the reference PF (344 nm). Smaller band gap (Eg) values in a range of 2.27-1.9 eV for newly designed molecules are observed which are very much reduced when compared to reference PF. Lowered exciton binding energies (Eb) and reorganization energies for the electron (0.004279-0.0103337 eV) as compared to PF reveal that our molecules display higher electron mobility rates, and hence, these small molecules can be used as proficient donor materials in high-performance organic solar cells (OSCs) and better hole transport materials (HTMs) for possible application in perovskite solar cells.

Bithieno Thiophene-Based Small Molecules for Application as Donor Materials for Organic Solar Cells and Hole Transport Materials for Perovskite Solar Cells.

This quantum mechanical study focuses on the designing of twelve (MPAM1-MPAM12) bithieno thiophene (BTTI) central core-based small molecules to explore optoelectronic properties as donor candidates for organic solar cells (OSCs) and hole transport materials (HTMs) accompanied by enhanced charge mobility for perovskite solar cells (PSCs). MPAM1-MPAM6 have been designed by the substitution of thiophene-bridged end-capped acceptors on both side terminals of reference (MPAR). MPAM7-MPAM12 are tailored by adopting the same tactic on one side terminal only. MPW1PW91/6-311G (d,p) has been employed for all computational simulations. MPAM12 revealed the highest λmax at 639 nm in dichloromethane (DCM) solvent with the lowest E g of 1.78 eV and dipole moment (20.74 D) in the solvent phase, showing excellent miscibility as compared to the reference. All designed chromophores (MPAM1-MPAM12) demonstrated higher estimated V OC and power conversion efficiency (PCE) when compared to MPAR, suggesting their prominent operational efficiency. Among all, MPAM4 manifested the highest PCE (47.86%). MPAM2 portrayed the highest electron mobility (0.0041573 eV) and MPAM3 exhibited the highest hole mobility (0.0047178 eV). The outcomes highlight the adequacy of the planned strategies, paving a new route for the development of small-molecule HTMs for PSCs and donor contributors for OSCs.

Nano-porous C4N as a toxic pesticide's scavenger: A quantum chemical approach.

The sensing affinity of C4N is the most fascinating topic of research due to its excellent chemical and electronic properties. Moreover, owing to the highly active porous cavity, C4N can easily accommodate foreign molecules. Herein, we studied the adsorption properties of carbamate insecticides (CMs) namely, Dimetalin (DMT), Carbanolate (CBT), Isolan (ISO) and Propoxur (PRO) using density functional theory calculations. All the results are calculated at widely accepted ωB97XD functional along with 6-31G(d, p) basis set. The calculated counterpoise corrected interaction energy of the reported complexes ranges between -20.05 and -27.04 kcal/mol, however, the interaction distances are found to be higher than 2.00 Å. The values of interacting parameters depict that the carbamate molecules are physisorbed via noncovalent interactions that can easily be reversible. Moreover, the binding of selected insecticides notably changes the electronic structure of C4N. The electronic changes are characterized by the energies of HOMO & LUMO, their energy gaps and CHELPG charge transfer. The charge density difference between C4N surface and carbamate pesticides are characterized by EDD and CDA analysis. Moreover, the ab initio molecular dynamic study reveals that the complexes are stable even at 500 K. The photochemical sensing properties of C4N are estimated by time dependent UV-Vis calculations. The high sensitivity of C4N towards considered analytes enable it to act as a promising sensor for toxic pesticides.

Alkaline earth metals (Be, Mg, Ca) doped hexamine complexant with enhanced electronic and nonlinear optical properties.

Organic complexant hexamine (hexamethylenetetramine, HMTA) is doped with alkaline earth (AE) metals, and new complexes are designed systematically to explore their nonlinear optical (NLO) properties by carrying out DFT calculations. Optimization of afresh designed geometries has shown their sufficient thermodynamic stability. Moreover, the energy band gap of pure HMTA is 10.62 eV which is reduced up to 2.63 eV for our doped complexes. This shows that alkaline earth metals are effective in enhancing the electronic properties of a system. Time-dependent DFT calculations are achieved, and results show that higher absorption maxima (λmax) along with small transition energies (ΔE) have significantly increased the hyperpolarizability (ß0) values (21,338-220,585 au). This higher hyperpolarizability is an elementary prerequisite for improved NLO response of a material. Transition density matrix (TDM) analysis, density of states (DOS) analysis, and electron density difference map (EDDM) studies are executed to get information about electronic distribution, crucial transitions, and electron transfer properties. As a result of these findings, it can be concluded that alkaline earth metal-doped HMTA might be a competitor for NLO materials with remarkable optical and electronic properties and better future applications in the field of optoelectronics.

Designing neodymium-doped hexamine complexant as novel IR NLO material with extremely large non-linear optical behavior.

A new complex named HMNd has been basically designed by doping rare-earth neodymium metal inside the hexamine surface HM. Density functional theory (DFT) calculations were carried out using B3LYP functional with split basis set GENECP to examine their geometrical, electronic, and non-linear optical properties of newly designed complex HMNd. After getting stable geometry of HMNd, its optoelectronic properties were compared with pure HM surface to check the influence of doping. HMNd revealed the obvious reduction in band gap energies from 8.4 eV (HM) to 1.79 eV (HMNd) as confirmed through DOS analysis. The highest hyperpolarizability and linear isotropic polarizability values of 6.8 × 105 a.u and 262.81 a.u respectively are perceived in HMNd. Electronic and thermodynamic stability of the designed complex has been confirmed through their vertical ionization and interaction energies. As revealed through the UV-visible analysis, doping with neodymium metal (HMNd) shifts the absorption to IR region with λmax of 2699.63 nm which leads towards the production of new materials. These upshots highlight the adequacy of designed complex providing gateway for designing new IR NLO materials in laser frequency conversion technology having usages in versatile fields.

Computational investigation of a covalent triazine framework (CTF-0) as an efficient electrochemical sensor.

In the current study, a covalent triazine framework (CTF-0) was evaluated as an electrochemical sensor against industrial pollutants i.e., O3, NO, SO2, SO3, and CO2. The deep understanding of analytes@CTF-0 complexation was acquired by interaction energy, NCI, QTAIM, SAPT0, EDD, NBO and FMO analyses. The outcome of interaction energy analyses clearly indicates that all the analytes are physiosorbed onto the CTF-0 surface. NCI and QTAIM analysis were employed to understand the nature of the non-covalent interactions. Furthermore, SAPT0 analysis revealed that dispersion has the highest contribution towards total SAPT0 energy. In NBO analysis, the highest charge transfer is obtained in the case of SO3@CTF-0 (-0.167 e-) whereas the lowest charge transfer is observed in CO2@CTF-0. The results of NBO charge transfer are also verified through EDD analysis. FMO analysis revealed that the highest reduction in the HOMO-LUMO energy gap is observed in the case of O3 (5.03 eV) adsorption onto the CTF-0 surface, which indicates the sensitivity of CTF-0 for O3 analytes. We strongly believe that these results might be productive for experimentalists to tailor a highly sensitive electrochemical sensor using covalent triazine-based frameworks (CTFs).

Impact of end capped modification on BT-CIC molecule for high-performance photovoltaic attributes: a DFT approach.

With the aim of utilizing structural modeling techniques to design efficient organic solar cells, a quantum chemical density functional theory (DFT) and its time-dependent DFT (TD-DFT) study have been carried out for the examination of the photovoltaic properties of four BT-ClC-based novel non-fullerene acceptor (NFA) molecules. The designed entities (BT1-BT4) have an A-π-D-π-A configuration with seven fused ring-based BDT central core and newly substituted peripheral acceptor moieties. The optical parameters (absorption maxima, light-harvesting efficiency, first excitation energies, and dipole moments), electronic properties (frontier molecular orbitals, density of states, and molecular electrostatic potential), and charge transfer characteristics (open-circuit voltage, transition density matrix, and fill factor) of the investigated molecules were evaluated using the selected B3LYP/6-31G (d,p) level of theory. The systematic computational analysis reveals that under the influence of terminal acceptor groups, there is an augmentation in the absorption range, and reduction in the band gap values. The electron withdrawing effect of acceptor moieties is evident from the electronic density distribution on the HOMO-LUMO orbitals, along with the density of state (DOS) graphs. Transition density matrix (TDM) analyses reveal consistent charge transfer in the newly devised entities. Reorganization energies computed for electron and hole are significantly lower than the reference, making the transfer of charge carriers efficient. Open-circuit voltage (Voc) of reported acceptor entities, theoretically computed with PTB7-Th donor, revealed maximum output. Furthermore, the estimated fill factor (FF) of the investigated molecules predicted an increase in power conversion efficiencies. Consequently, all the computed parameters favor the applicability of our designed molecules in the field of organic photovoltaics by virtue of their excellent charge mobilities, increased absorption maximum values, and reduced band gaps.