Adel A. El-Azhary

Microwave synthesis of graphene sheets supporting metal nanocrystals in aqueous and organic media

We have developed a facile and scalable chemical reduction method assisted by microwave irradiation for the synthesis of chemically converted graphene sheets and metal nanoparticles dispersed on the graphene sheets. The method allows rapid chemical reduction of exfoliated graphite oxide (GO) using a variety of reducing agents in either aqueous or organic media. It also allows the simultaneous reduction of GO and a variety of metal salts thus resulting in the dispersion of metallic and bimetallic nanoparticles supported on the large surface area of the thermally stable 2D graphene sheets.

A coupled-cluster study of the structure and vibrational spectra of pyrazole and imidazole.

Harmonic force fields were calculated at the corresponding optimized geometries for pyrazole and imidazole at the HF, B3LYP, MP2, CCSD and CCSD(T) levels using the 6-31G* basis set and at the HF and B3LYP levels using the cc-pVTZ basis set. The agreement between the calculated and experimental geometries by the CCSD and CCSD(T) methods was generally similar to that obtained with the B3LYP and MP2 methods. The force fields were scaled using one-scale-factor (1SF), 3SF and 7SF scaling schemes. The scale factors were varied with respect to the experimental frequencies. Using 7SF scaling, the root-mean-square (RMS) deviation of the calculated frequencies from the experimental frequencies by the HF, B3LYP, MP2, CCSD and CCSD(T) methods and the 6-31G* basis set was 16, 7, 13, 11 and 11 cm(-1), respectively. This shows that the B3LYP method is preferred for force field calculations over the perturbative MP2, CCSD and CCSD(T) methods. Using 1SF scaling, the CCSD(T) scale factor was 0.931, the highest among the five methods used but close to that obtained with the B3LYP method and the cc-pVTZ basis set with lower RMS deviation.

Conformational and vibrational analysis of 18-crown-6–alkali metal cation complexes

Conformational analysis was performed for the 18-crown-6-alkali metal cation complexes, 18c6-AMCCs, using the CONFLEX method. The number of predicted conformations of the 18c6-Li+, Na+, K+, Rb+ and Cs+ complexes was 10, 24, 15, 9 and 4 conformations, respectively. Electronic and geometrical structures were calculated for the predicted conformations at the HF, B3LYP, CAM-B3LYP, M06 and MP2 levels. Binding energies and enthalpies of the ground state conformations were also calculated. Vibrational, IR and Raman, spectra of free 18c6 and 18c6-AMCCs were measured. Comparison between the calculated vibrational frequencies using multi-scale-factor scaling of the B3LYP force field and the experimental vibrational frequencies predicted that the 18c6-K+, Rb+ and Cs+ complexes exist in the D3d, C3v and C3v conformations, respectively. It was also predicted that the 18c6-Na+ complex exists in a D3d-like conformation. It was not possible to identify in what conformation the 18c6-Li+ complex exists.

Conformational study of the structure of 18-thiacrown-6.

Conformational analysis was performed for 18-thiacrown-6 (18t6) using the CONFLEX method and the MMFF94s force field. Computations were performed for some of the low energy conformations at the HF, B3LYP, CAM-B3LYP, M06, M06L, M062x, M06HF and MP2 levels. The computations were also performed using the DFT-D3 method along with the TPSS and PBE functionals. The study predicted a new C2 conformation as the ground state conformation of 18t6. This new C2 conformation is more stable than the experimentally known solid state conformation by 4.7 kcal/mol at the MP2/6-311G** level. This conformation has all of the SCCS dihedral angles adopt exodentate structure. However, the experimentally known conformation of the solid phase has two of the SCCS dihedral angles violating this exodentate rule. It was concluded that for 18t6 stability a linear dihedral SCCS angle requirement is more important than a gauche CSCC dihedral angle requirement.

A G3 study of the structure of carbon-nitrogen nanoclusters.

Possible structures of the carbon-nitrogen clusters of the form C(m)N(n) (m = 1-4, n = 1-4, m + n = 2-5) were predicted for the neutral, anion, and cation species in the singlet, doublet, and triplet states, whenever appropriate. The calculations were performed at the G3, MP2(fc)/6-311+G*, and B3LYP/6-311+G* levels of theory. Several molecular properties related to the experimental data--such as the electronic energy, equilibrium geometry, binding energy, HOMO-LUMO gap (HLG), and spin contamination --were calculated. In addition the vertical electron attachment, the adiabatic electron affinity, and vertical ionization energy, of the neutral clusters were calculated. Most of the predicted lowest energy structures were linear, whereas bent structures became more stable with the increase of the cluster size and increase of the number of the N atoms. In most of the predicted lowest energy structures, the N atom prefers the terminal position with acetylenic bond. The calculated BE of the predicted clusters increases with the increase of the cluster size for the neutral and cation clusters but decreases with the increase of the cluster size for the anion clusters. The predicted clusters are characterized by high HLG of about 11 eV on the average, with that of the anion clusters is smaller than that for the neutral and cation clusters. It is concluded then that the anion clusters are less stable than the corresponding neutral and cation clusters. Finally, the N(2) loss reaction is treated.

Experimental and theoretical study of the vibrational spectra of 12-thiacrown-4 and 18-thiacrown-6, evaluation of the performance of the different anharmonic force fields compared to the scaled quantum mechanical force fields.

We report, to the best of our knowledge, for the first time the vibrational, IR and Raman, spectra of 12-thiacrown-4 (12t4) and 18-thiacrown-6 (18t6). To predict in what conformation 12t4 and 18t6 exist, for the vibrational analysis of both molecules and to assess the performance of the different computational methods for the accurate prediction of the vibrational frequencies of relatively large molecules, the computations were done using the harmonic and anharmonic force fields using the 6-31G* and 6-311G** basis sets. The computations were performed at the HF, B3LYP, CAM-B3LYP, BLYP, BP86, G96LYP, PBE1PBE, TPSSH and MP2 levels. Comparison was made between the calculated and experimental vibrational frequencies as indicated by the root-mean-square (rms) deviations, using either the unscaled and scaled harmonic vibrational frequencies and, unscaled, anharmonic vibrational frequencies. For the harmonic vibrational frequencies two scaling schemes were used. One uses one-scale-factor (1SF) scaling and the other uses 8SF scaling. In terms of the vibrational analysis of 12t4 and 18t6, the report confirms the solid state X-ray structure of D4 of 12t4 and C2 of 18t6. It is concluded that a lower rms deviation is obtained using 1SF scaled harmonic vibrational frequencies at even the HF/6-31G* level than using anharmonic vibrational frequencies at the MP2/6-311G** level. The CAM-B3LYP method showed some improvement over the traditional B3LYP method.

Theoretical study of the structure and vibrational spectra of the Ci(2) conformation of 18-crown-6

Optimized geometries of 18-crown-6 (18ce6) were calculated at the HF/6-31G* and B3LYP/6-31G* levels of theory for the D3d, Ci(1) and Ci(2) conformations. At the B3LYP level, the Ci(2) optimized geometry was higher in energy by 23.3 and 18.8 kcal mol(-1) than the Ci(1) and D3d optimized geometries, respectively. Harmonic force field, vibrational frequencies and IR absorption intensities were calculated at the corresponding optimized geometry at the B3LYP level for the Ci(2) conformation. Scaled Ci(2) frequencies were compared with the experimental frequencies of free 18ce6, Ci(1) conformation, and 18ce6-urea complex, Ci(2) conformation. This comparison showed possible misassignments in the fundamental vibrational frequencies of 18ce6.

Conformational Study of the Structure of dibenzo-18-crown-6. Comparison with 18-crown-6

We report for the first time the conformational analysis of dibenzo-18-crown-6, db18c6. The conformational search was carried out using the CONFLEX conformational search method of cyclic molecules. Energies were calculated for the low-lying predicted conformations at different levels of theory up to the G3MP2 level. At the G3MP2 level, the predicted ground state (GS) conformation was more stable than the experimental conformation by only 1.60kcal/mol. Strong similarity was found between the GS structure and experimental conformations of db18c6 and 18-crown-6, 18c6. The GS and experimental conformations of db18c6 are non-planar. This allows db18c6 to exist in optically active enantiomers. Similar to 18c6, it was concluded that the db18c6 structure is stabilized by intramolecular hydrogen bond. We also performed the computations for the water and chloroform solution phase, where the same conformation was predicted as the GS conformation.

Electronic structure and properties of neutral, anionic and cationic silicon-nitrogen nanoclusters.

We performed a G3 investigation of the possible stable structures of silicon–nitrogen SinNm clusters where m = 1–4, n = 1–4, m + n = 2–5. We considered the neutral, anionic and cationic molecular species in the singlet, doublet and triplet states, as appropriate. For neutral clusters, our data confirm previous DFT and post Hartree-Fock findings. For charged clusters, our results represent predictions. Several molecular properties related to the experimental data, such as the electronic energy, equilibrium geometry, binding energy (BE), HOMO–LUMO gap (HLG), and spin contamination