International Journal of Quantum Chemistry最新文献

Unsymmetrical xanthene dyes are a hybrid structure of two symmetrical xanthene dyes. Therefore, are the structural, spectral, electronic, linear, and non-linear optical (NLO) properties of unsymmetrical xanthene dyes comparable to, distinct from, or better than those of their parent symmetrical xanthene dyes? This study provides a detailed analysis of unsymmetrical and symmetrical xanthene dyes using the Density Functional Theory (DFT) and Time-dependent (TD)-DFT methods. DFT study demonstrated that symmetrical xanthene dyes are energetically more stable and exhibit BLA values lower than unsymmetrical xanthene dyes. Moreover, symmetrical xanthene dyes show destabilized energy of HOMO, LUMO, and lower LUMO–HOMO energy gap than unsymmetrical xanthene dyes. Vertical excitation calculated from the TD-DFT method shows reasonable agreement with experimental absorption. However, unsymmetrical xanthene dyes with higher dipole moments and hyperpolarizability show superior NLO properties.

Developing novel non-fullerene acceptors (NFAs) by modifying A₁-DA₂D-A₁ Y6 molecules is an effective strategy to improve the energy conversion efficiency of organic solar cells (OSCs). To understand the mechanism of regulating the photovoltaic performance by modifying the central fused ring, end group, and inner chain segments of Y6, D18:Y6, D18:AQx-2, D18:AQx-18, D18:BTIC-γ-2CN and D18:Z9 OSCs were systematically studied based on extensive quantum chemistry calculations, and the impacts of different chemical groups on molecular properties and photovoltaic performances were analyzed. The substitution of benzothiadiazole in the central fused ring of Y6 with quinoxaline, substituting quinoxaline with phenazine, introducing benzonitriles at the end group, and phenyl groups into inner side chains enhance molecular skeleton planarity, slightly elevate the highest occupied molecular orbital energy and the lowest excitation energy, and enlarge light absorption efficiency. Introducing quinoxaline and phenyl groups causes the reduction of the electrostatic potential difference between D18 and NFAs; on the contrary, introducing phenazine and benzonitriles induces the opposite effects. Introducing quinoxaline and phenazine generates negligible effects on charge transfer (CT) energies, whereas introducing benzonitrile and the phenyl group increases CT energies. Introducing phenazine and the phenyl group generates sufficient energy difference between local excitation and CT to conquer exciton binding. The rate constants calculated using Marcus theory indicate that all molecular modifications of Y6 reduced exciton dissociation rates. However, the introduction of benzonitrile increases CT and suppresses charge recombination rates. The results reveal the inherent relationship between molecular structure and photovoltaic performance, providing the theoretical basis for the design and development of NFAs.

Density functional theory (DFT), molecular dynamics simulations (MDS), mass loss (ML), and electrochemical studies were performed to assess the corrosion preventive ability of oxadiazole derivatives, 1-(1((5-phenyl-1,3,4-oxadiazol-2-yl)methyl)-1H-benzo[d]imidazol-2-yl)-3-(thiophene-2-yl)prop-2-en-1-one (PBTP) and 3-(furan-2-yl)-1-(1((5-phenyl-1,3,4-oxadiazol-2-yl)methyl)-1H-benzo[d]imidazol-2-yl)prop-2-en-1-one (FPBP) on N80 steel (NS) in 15% HCl medium. The compounds PBTP and FPBP exhibited corrosion preventive ability of 97.13% and 94.16% for NS in the presence of 250 ppm concentration at 298 K temperature. Corrosion inhibition efficiency of both compounds increases with increase in concentration and decreases with increase in temperature. Adsorption of both inhibitors followed Langmuir adsorption isotherm. Potentiodynamic polarization studies suggested that both inhibitors behave as mixed type (anodic as well as cathodic) inhibitors. The analysis of field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and x-ray photoelectron spectroscopy (XPS) verified the development of the inhibitor protective layer at the NS surface to prevent its corrosion. The computational studies are in good agreement with the experimental results.

The molecular structure of phenyl-substituted cyclopropanecarboxylic acid (PSCCA, C₁₂H₁₄O₂; 3-methyl-3-phenylcyclobutane-1-carboxylic acid) was determined using nuclear magnetic resonance (NMR), infrared spectroscopy (IR), and X-ray crystallography techniques. Following structural confirmation, its molecular geometry was optimized at the Density Functional Theory (DFT) level. The van der Waals interactions were accurately accounted for using the DFT-D3 method in the CP2K program. Understanding the adsorption behavior of organic molecules on metal surfaces is of great significance for applications in catalysis, sensor design, surface functionalization, and corrosion prevention. In this context, the adsorption properties of the PSCCA molecule on Al and Cu surfaces were investigated in detail using DFT-based CP2K calculations. By optimizing different adsorption configurations, the binding energies of the most stable structures were calculated and compared. The obtained results indicate that the PSCCA molecule strongly binds to both Al and Cu surfaces, with a higher adsorption energy on the Al surface compared to the Cu surface. In addition, Mulliken population analysis revealed distinct electronic charge transfer characteristics upon adsorption, with substantially stronger electron transfer observed on the Cu(111) surface due to enhanced d-band–ligand orbital hybridization. This electronic behavior correlates with the adsorption strength and highlights the critical role of metal electronic structure in governing surface interactions. Electron density difference analyses suggest that PSCCA interacts with both surfaces via a physisorption mechanism. Furthermore, assessments in the context of surface inhibitor efficiency reveal that PSCCA has the potential to passivate active surface regions and hinder surface reactions. Analyses conducted under different pH conditions indicate that the inhibitory effect of PSCCA is particularly pronounced in acidic environments. These findings suggest that PSCCA, exhibiting higher adsorption energy and stability on the Al surface, can be considered an effective protective agent and may play a crucial role in the design of metal–organic interfaces.

Single-atom catalysts (SACs) with high activity and selectivity are regarded as excellent OER catalysts, but easily corroded under acidic environment. Here, we employed density functional theory (DFT) calculations to design a series of SACs protected by twisted bilayer graphene (tBLG) “chainmail.” Charge transfer analysis showed that the carbon layer could serve as an intermediate between transition metal atom and reactants. In addition, rotation operation on bilayer graphene was applied to further enhance the catalytic performance. Thermodynamic free energy diagrams of eight types metal atoms and five rotation angles were systematically discussed. A volcano plot of overpotentials among all the studied single metal atom twisted bilayer graphene catalysts can be described by ($��\Delta �G_{�O�*�}�-�\Delta �G_{�\mathrm{OH}�*�}�$). The designed Ni-tBLG catalyst (rotation angle is 21.8°) exhibited the best performance with the lowest OER overpotential of 0.35 V. These results revealed that the selected single metal atom twisted bilayer graphene catalysts with high activity and stability could be treated as efficient OER catalysts.

This study addresses the issue of organic dye contamination in freshwater by examining the removal of methyl orange (MO) dye using graphitic nanofibers (GNFs) synthesized on cobalt chloride alcogel (CCA). The effect of pH, contact time, adsorbate dose, and adsorbent mass on MO dye adsorption was investigated. GNFs were synthesized via chemical vapor deposition (CVD) on CCA and treated with 25% (w/v) aqueous hydrofluoric acid (HF) to remove silica contents from the sample. Characterizations of the material were performed using XRD, SEM, TEM, and Raman spectroscopy. XRD confirmed the presence of graphitic carbon and metallic cobalt along with minor cobalt oxide phases, while Raman spectroscopy indicated the defective nature of GNFs. SEM and TEM verified the predominant fibrous morphology of the prepared sample. Adsorption studies revealed that the HF-treated material exhibited superior adsorption capabilities compared to untreated material. The better performance of the HF-treated composite was attributed to synergistic effects due to increased defect sites, metallic positive centers, and extended pi-pi interactions. Kinetic regression results indicated that the pseudo-second-order kinetic model best describes the adsorption process. The Langmuir adsorption isotherm suggested the monolayer adsorption of adsorbate on the adsorbent surface. In addition, the study demonstrated that approximately 81 wt% of the material comprised GNFs grown on CCA via CVD at 650°C. Furthermore, the adsorption process was controlled by both adsorbate mass and concentration, highlighting the potential of GNFs synthesized on CCA as effective adsorbents for removing organic pollutants from aqueous solutions in environmental applications.

The ongoing advancement of electronic devices has catalyzed research into rechargeable battery technologies. Zinc-ion batteries (ZIBs) present a promising alternative to lithium-ion batteries owing to their cost-effectiveness, high energy capacity, and enhanced safety features. This study employs first-principle calculations to assess the viability of utilizing monolayer ZrSe₂ as an electrode material for ZIBs. The findings reveal that ZrSe₂ demonstrates considerable stability, with a diffusion barrier of 0.061 eV when employed as an anode material for ZIBs. Furthermore, the theoretical capacity of monolayer ZrSe₂ is projected to reach 430.10 mAh/g. These theoretical insights indicate that monolayer ZrSe₂ has the potential to serve as an efficient anode material for ZIBs.

The low-cost and highly active FeN₄C single-atom catalyst is currently one of the most promising oxygen reduction catalysts for replacing the precious metal catalysts in fuel cells. The electron occupation states of Fe 3d orbitals have been proved to play a determining role in the catalytic activity of FeN₄C. Herein, by adding the second transition-metal atom M to form FeMN₆C, we modulate the 3d-orbital splitting and spin states of Fe to uncover the spin effects on the adsorption energies of oxygen-containing intermediates and catalytic activity. The results reveal that the introduction of M gives rise to various electron occupation states and magnetic moments of the Fe atom, tuning the catalytic activity of FeN₄C. Among them, FeRhN₆C and FePdN₆C have low theoretical ORR overpotentials of 0.41 and 0.42 V. It is found that there is a volcano relation between the spin moments of Fe and the adsorption energies rather than the linear relation reported in other work.

Quaternary semiconductors based on copper offer special characteristics such as strong thermoelectric stability and tunable optical response. Here, the multifaceted association between the structure, optoelectronic and transport properties of direct band gap novel BaCuMF (M = S, Se) quaternary semiconductors was examined employing the recognized density functional theory. The formation energies show the stability of these materials and are much lower than the corresponding elemental hulls. Strong correlations were found between the ionicity in the Ba–X bindings and the formation energy, suggesting that these materials share a low formation energy with other ion bindings. BaCuSF showed greater resistance than BaCuSeF, which led to differences in the strength of bonds between the atoms. With TB-mBJ and PBE-GGA, the band structure estimates are 2.69, 1.28 for BaCuSF, and 2.64, 1.62 eV for BaCuSeF, respectively. These materials were found advantageous for tunable device applications due to their wide absorption spectrum. The significant and remarkable thermoelectric properties of the examined materials indicate their suitability for thermoelectric applications. Their potential application in cutting-edge optoelectronic devices can be established by the current work, opening up innovative technological possibilities.