AbstractBased on the improved multiparameter exponential‐type potential (IMPET), an extended IMPET (EIMPET) potential has been suggested to reduce the discrepancy between the calculated and experimental values, improving the accuracy near the equilibrium and in the asymptotic region. The average fitting deviation δav and Root‐Mean‐Square (RMS) error is used to evaluate the performance of the potential which generates potential energy curves (PECs) and vibrational energy levels for ClF‐A(3Π1), CP‐X2Σ+, ICl‐X1Σ+, IBr‐X1Σ+, CO‐X1Σ+, and 6Li2‐X1Σ+ molecules that agree better with the Rydberg‐Klein‐Rees (RKR) data than Morse, Huxley‐Murrell (HM) and IMPET potentials. This work provides a reference for the construction and improvement of potential energy functions for diatomic molecules.

AbstractThe stabilities, mechanical, electronic, and magnetic properties of the new equiatomic quaternary Heusler alloy (EQHA) RuTiCrSi were investigated using the Kohn‐Sham DFT (KS‐DFT) calculations within the generalized gradient approach (GGA), the modified version of the exchange potential introduced by Becke and Johnson in addition to the GGA (mBJ‐GGA), and Heyd‐Scuseria‐Ernzerhof (HSE06) hybrid functional. The ground‐state equilibrium energy reveals that the ferromagnetic with type 2 structure is the more stable. The RuTiCrSi is energetically, mechanically, and dynamically stable. The calculated self‐consistent total magnetic moment is 2 μB and agrees well with the Slater‐Pauling rule of . The electronic structure results from mBJ‐GGA and HSE06 functionals show a half‐metallic behavior. A high Curie temperature is obtained using the mean‐field approximation. The thermoelectric response was calculated using the semi‐classical Boltzmann transport equation under constant relaxation time. The maximum value of Seebeck coefficient is observed at the ambient temperature of . It was also observed that the power factor increases significantly as temperature rises. Therefore, the new EQHA RuTiCrSi seems to be a potential candidate for spintronic thermoelectric applications.

AbstractDriven by the goal of establishing a fossil‐fuel‐free and nuclear‐power‐free economy based on renewable energy, metal‐air batteries are regarded as promising energy conversion and storage devices. Developing efficient oxygen reduction reaction (ORR)/oxygen evolution reaction (OER) bifunctional electrocatalysts for the air electrode of metal‐air batteries is becoming increasingly important. In this work, 36 transition metal (TM) single‐atom catalysts are designed based on MXenes Ti2CT2 with different surface terminal atoms (T = O, S, Cl), and their ORR/OER catalytic activity and stability are evaluated by the density functional theory. Ni@Ti2CO2, Pd@Ti2CS2, and Co@Ti2CCl2 are found to exhibit good catalytic activity with ORR/OER overpotentials of .54 V/.62 V, .59 V/.29 V, .44 V/.40 V. The aggregation behavior of three catalysts is estimated by comparing the average binding energy of one, two, three, and four TM atoms anchored on Ti2CT2. This work cannot only provide a theoretical guide to develop bifunctional single‐atom catalysts, but also help us understand the effect of terminal atoms on the electronic structures and catalytic activity of TM@Ti2CT2.

AbstractIn this work, by first‐principles calculations, we investigate the structural, photoelectric, and catalytic properties of g‐ZnO/Hf2CO2 vdW heterostructures to explore highly efficient photocatalysts of water splitting. Results show that the AA‐stacking g‐ZnO/Hf2CO2 vdW heterostructure (AA‐HS) with an indirect bandgap of 1.738 eV has a typical type‐II band alignment, which is benefit to effectively separate the photogenerated carriers into different layers and prevent their recombination. The conduction band minimum (CBM) and valence band maximum (VBM) of AA‐HS straddling the water redox potentials makes it satisfies the requirements of photocatalytic water splitting at pH = 7. In addition, to evaluate the photocatalytic performance of AA‐HS during oxidation evolution reaction (OER) process in water splitting, we calculated the change of Gibbs free energies of the intermediates on heterostructure under different conditions. Results show the Gibbs free energy decreases continuously at pH = 7 and U = 1.93 V. What's more, the AA‐HS has good sunlight‐absorption ability. External biaxial strain is not conducive to improving catalytic performance of AA‐HS.

AbstractWe present our results of the spin‐polarized calculations on the structural, magneto‐electronic, thermodynamic, and thermoelectric properties of vacancy‐ordered double perovskites A2OsX6 (A = Rb/Cs; X = Cl/Br). We utilized the Wu‐Cohen generalized gradient approximation (Wu‐GGA) and the mBJ scheme to determine a more reliable electronic structure. The compounds exhibit negative formation energy, suitable tolerance factor, and a stable phonon spectrum, indicating their stability. The compounds show half‐metallicity, acting as semiconductors with direct band gaps between 2 and 3 eV in the spin‐up orientation while metallic in the spin‐down. Each compound shows a total spin magnetic moment of 2.00 μB per formula unit, with Os‐t2g states contributing the most (~1.5 μB). The computed thermoelectric coefficient indicates the usability of these compounds across a wide temperature range (200–800 K) with high electrical conductivity and low electronic thermal conductivity. The compounds exhibit high Seebeck coefficient and figure of merit (ZT), making them suitable for thermoelectric applications. With ferromagnetic and half‐metallic characteristics, these compounds could be promising candidates for spintronics, thermoelectronic, and data storage applications.

AbstractIn this study, we introduce a novel definition for the electrophilic descriptor. Following the proposal of other researchers, the foundation of our approach lies in expanding the change in the energy of an electronic system using a third‐order Taylor series, leading to the integration of hyperhardness into the formulation of the electrophilic descriptor. To validate our results, we conducted a comparative analysis of reactivity sequences among 35 electrophilic systems with known reactivities, as reported in external experimental studies. The electrophilic descriptor demonstrated a remarkable ability to accurately replicate the relative reactivities of the compounds under consideration, surpassing predictions based solely on the electrophilicity index. These findings underscore the significance of incorporating hyperhardness as a crucial reactivity descriptor. Additionally, our study provides interesting insights into the interpretation of this concept.

AbstractTessellations of antikekulenes are of interest from the standpoints of antiaromaticity, ring currents, unusual ‐electron characteristics, magnetism and their highly reactive nature. Although precursors of antikekulenes have been synthesized, up to now synthesis of antikekulenes has been proven to be formidably difficult. Yet they are predicted to have intriguing properties and their antiaromatic nature together with a combination of four and six‐membered rings makes them intriguing candidates for theoretical indices. In the present study, we have computed the topological indices of antikekulene by employing graph‐theoretical cut methods that simplify the parent tessellations of antikekulenes into simpler graphs. We have derived exact mathematical expressions of several topological descriptors for hexagonal and rectangular antikekulene structures. Furthermore we have obtained the graph‐spectral properties, algebraic structure counts, resonance stabilization and delocalization energies as well as nuclear magnetic resonance and electron spin resonance spectroscopic patterns of the two tessellations of antikekulenes.

AbstractComputational investigation on the low‐lying photo‐excited states of N‐tert‐butyl‐α‐phenylnitrone (PBN), a well‐known spin‐trap agent, has revealed its photo‐product (oxaziridine) formation channel. The S0‐S2 vertical excitation in PBN is subsequently followed by a non‐radiative decay pathway through S2/S1 and S0/S1 conical intersections (CIs) with CNO‐kinked structures, situated around 23 kcal/mol and 45 kcal/mol below the vertically excited S2 state, respectively. The reverse photo‐process of PBN formation involves photo‐excitation of oxaziridine to its S2 and S3 photo‐excited states. The forward photo‐isomerization leads to the trans‐oxaziridine with a backside CNO kink (trans‐OXB) while the reverse path studied by us, connects its front‐side CNO‐kinked analogue (trans‐OXF) with the PBN. Our search for the reverse thermal reaction paths from these two oxazirdines has led to their corresponding transition states, one at 35 kcal/mol and the other at 27 kcal/mol above trans‐OXF and trans‐OXB geometries, respectively. They lead to two different isomers (E and Z) of PBN which supports the reported nature of products from the trans‐oxaziridine in this thermal reaction. The inversion path of the chiral nitrogen atom of this N‐tert‐butyl‐oxaziridine (barrier 21 kcal/mol) has also been tracked. This reaction path has been compared with that of the N‐methyl (barrier 30 kcal/mol) and N‐acyl (barrier 10.5 kcal/mol) oxaziridine analogues.

AbstractThis research work investigates the structural, electronic, optical, and thermoelectric characteristics of VFeZ (Z = N and P) half‐Heusler compounds. The study employs the full‐potential linearized augmented plane wave (FP‐LAPW) method integrated into the WIEN2K algorithm, serving as the underpinning framework for density functional theory (DFT) analysis. In the study, we use the PBE generalized gradient approximation (PBE‐GGA) to identify numerous parameters associated with structural and elastic properties. Lattice parameter results are in agreement with previous outcomes. Moreover, computed elastic parameters satisfy the criterion for stability. In the cubic structure VFeZ (Z = N and P) is ductile, to enhance the computations of electronic characteristics, Tran and Blaha's modified Becke‐Johnson potential (TB‐mBJ) is used. Our simulations demonstrate that the materials exhibit semiconductor behavior, with a direct band gap for VFeZ (Z = N and P). Strong UV absorption is found via optical experiments suggest compounds are suitable for optical application. Furthermore, study of the thermoelectric properties suggests its application in the thermoelectric generators.

AbstractDiatomic molecules , are common compositions in plasmas using the helium as the working gas, and play key roles in quenching O2 and N2. However, the potential energy curve (PEC) of the first state obtained at the CASSCF level of theory is not accuracy and data of higher excited states of are lacking. Here, we calculated PECs of four excited states of and nine lowest electronic states of by employing CASSCF+MRCI/Aug‐cc‐pV5Z and CCSD(T)/Aug‐cc‐pV5Z level of theory with sample internuclear distance interval of 0.005 Å. PECs were extrapolated to the complete basis sets. There are double local maxima in PECs of three excited states , , . The machine learning method based on the Gaussian process was used to interpolate and extrapolate the PECs, and then vibrational wave functions are solved numerically. This ab initio investigation provided rotational‐vibrational constants and new data for experimental research in the future.