Showing papers by "Naveen Kosar published in 2019"
TL;DR: In this article, a series of inorganic electrides (Li2F, Li3O and Li4N) are designed by doping of Al12P12 nanocluster with superalkalis and studied through density functional theory (DFT) for their geometrical, electronic and nonlinear optical properties.
89 citations
TL;DR: In this article, the effect of different superalkalis and different doping positions on the nonlinear optical response of B12P12 nanostructures was investigated using density functional theory (DFT).
Abstract: Three series of compounds Li2F@B12P12, Li3O@B12P12 and Li4N@B12P12 are theoretically designed and investigated for their nonlinear optical response using density functional theory (DFT). Computational results reveal that isomers VIII and X are inorganic electrides whereas the others are excess electron systems. Interaction energies reveal that these systems are quite stable and superalkalis are chemisorbed on the nanocage. Doping of a B12P12 nanocage with superalkali brings a considerable increase in the first hyperpolarizability response of the system. The highest first hyperpolarizability (β0 = 3.48 × 105 a.u.) along with good ultraviolet transparency is observed for isomer III of Li2F@B12P12. Moreover, all three series of compounds are systemically studied for the effect of different superalkalis and different doping positions on the nonlinear optical response. This study will be advantageous for promoting the potential applications of the fullerene-like superalkali doped B12P12 nanostructures in new types of electronic nanodevices and high-performance nonlinear optical materials with good ultraviolet transparency.
59 citations
TL;DR: In this article, the effect of doping different superalkalis (Li3O, Na3O and K3O) over Zn12O12 nanocages is also studied.
Abstract: Fabrication of stable nonlinear optical materials is highly demanding due to their widespread applications in optical and optoelectronic devices. Novel inorganic complexes are theoretically designed and investigated by doping superalkalis on Zn12O12 cluster. The results reveal that doping causes shifting of excess electrons from superalkalis towards Zn12O12 cluster and enhances the NLO properties of these isomers. Moreover, the effect of doping different superalkalis (Li3O, Na3O and K3O) over Zn12O12 nanocages is also studied. All the isomers have shown excellent NLO response and are transparent under ultraviolet region of workable laser conditions. Comparative analysis reveals that hyperpolarizability shows monotonic dependence on atomic number of metal atom in the superalkalis. K3O@Zn12O12 exhibits the highest first hyperpolarizability (βo) value of 394,217 au. The band gap is reduced up to 70% as compared to pristine nanocage, making them n-type semiconductors. This study provides a pathway for designing thermally stable inorganic complexes as potential precursors for high-performance NLO materials.
57 citations
TL;DR: In this article, the geometric and electrochemical properties of Na/Na+ with both B12P12 and Al 12P12 nanocages were investigated to investigate the effect of neutral or ionic Na on the geometric properties.
23 citations
TL;DR: Benchmark DFT studies on C–CN homolytic cleavage indicate that electron withdrawing groups (EWGs) lower the BDE, while electron donating groups (EDGs) increase the Bde of the C–CN bond.
Abstract: Nitriles are important chemical species in organic transformations, material chemistry, and environmental sciences. Nitriles are used as cyanating reagents in many organic reactions, where the C–CN bond dissociation has an important role. The reactivity of nitriles can be better understood by studying the bond dissociation energy (BDE) of the C–CN bond. In this benchmark study, homolytic cleavage of the C–CN bond in 12 nitrile compounds is studied. Thirty-one functionals from eight different DFT classes along with three types of basis sets are employed. Theoretical results are compared with the available experimental data. Based on statistical outcomes, the CAM-B3LYP functional of the range separated hybrid GGA class with Pople 6-311G(d,p) basis set provides the most accurate results for calculating the BDE of the C–CN bond. The mean absolute error (MAE) value is 0.06 kcal mol−1, whereas standard deviation (SD) and Pearson’s correlation (R) are 2.79 kcal mol−1 and 0.96, respectively, when compared with experimental data. The substitutional effect on the homolytic cleavage (BDE) of respective bonds in differently substituted nitriles is also investigated. The BDE results indicate that electron withdrawing groups (EWGs) lower the BDE, while electron donating groups (EDGs) increase the BDE of the C–CN bond. The NBO and HOMO–LUMO orbitals analyses are also performed to further elaborate the variational BDE patterns of C–CN bond cleavage.
17 citations