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CONTEXT: This work focuses on the study of six molecules composed of the TetraAmineLithium (TALi+) and TetraAmineSodium (TANa+) structures linked with the anions H-, Li- and Na-. The NLO results obtained by these calculations showed significant values of static first hyperpolarizabilities (ßtot) ranging from 8.74 * 10-30 to 691.99 * 10-30 esu. The two molecules TALi-Li and TALi-Na gave the highest values of static ßtot equal to 563.20 and 691.99 * 10-30 esu respectively and static second hyperpolarizabilities (γav) of 680.02 and 779.05 * 10-35 esu. The highest dynamic first hyperpolarizabilities (ß||) values are around 1474080.00 * 10-30 esu and 6,145,080.00 * 10-30 esu at 720 nm lasers and which are attributed to the two molecules TANa-Li and TANa-Na respectively. Four molecules have push-pull behavior where the anions are donor groups, the Li+-NH3 and Na+-NH3 groups are acceptor groups and a bridge composed by the three remaining NH3 ligands. The maximum wavelengths (λmax) in vacuum and in the presence of solvents for all molecules are in the range 240 to 870 nm. METHOD: The software used in this study is Gaussian 16. The optimizations of the molecules were calculated by B3LYP-D3/6-31 + + G(d,p). The static first hyperpolarizability (ßtot) was calculated by different functionals: CAM-B3LYP, LC-wPBE, LC-BLYP, M11, wB97X, HSEh1PBE and M06-2X and the MP2 method, the basis-set used is 6-31 + + G(d,p). Other calculations of static ßtot were carried out by the CAM-B3LYP functional combined with several basis-sets: 6-31G(d,p), 6-31 + + G(d,p), cc-pVDZ, AUG-cc- pVDZ, 6-311G(d,p), 6-311 + + G(d,p), cc-pVTZ and AUG-cc-pVTZ. The calculations of the first (ß||) and second (γ||) hyperpolarizabilities in second harmonic generation (SHG) were calculated by CAM-B3LYP/6-31 + + G(d,p). The delocalization energies (E(2)) were determined by the NBO approach and calculated by the same functional and basis-set cited before. The solvation Gibbs energies (ΔGsolv) were calculated using the implicit SMD model. Maximum wavelengths (λmax) and oscillator strengths ([Formula: see text]) were calculated by TD-CAM-B3LYP/6-31 + + G(d,p) in the presence of the implicit CPCM model.
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CONTEXT: This article is based on the study of pyrrolic derivatives and their oligomers. Knowing that, pyrrolic derivatives are widely studied on an industrial scale. The aim of this work is to find pyrrolic derivatives having the same physicochemical characteristics such as the pyrrolic edifice. Six derivatives were studied by substituting the hydrogens in the ß position of the pyrroles with the following radicals: -CHO, -Cl, -CN, -NO, and -OH. The study was carried out theoretically using ab initio and density functional of theory (DFT) methods. In the first step, molecules of four units were taken into consideration in order to make the comparison between them. This comparison showed that the majority of molecules exhibited high intramolecular charge transfer (ICT) compared to the molecule composed of four pyrrolic units (OP4), and also exhibited strong nucleophilic and electrophilic characteristics. Natural bond orbital (NBO) analysis has shown continuous ICT mechanisms for certain molecules. The studied derivatives showed good solvation in several solvents compared to OP4. The molecules substituted by the radicals -CHO, -CN, -OH, and -NO generated several peaks in the excited states, which is the opposite case for the other molecules with a single peak. The effects of chain elongation revealed exponential equations generated by the two parameters energy gaps (ΔEH-L) and maximum wavelengths (λmax) as a function of the number of units (n). These equations were used to predict the maximum and minimum values of the above parameters for more elongated oligomers. METHOD: The software used to make the calculations is Gaussian 16. All geometries were calculated by B3LYP functional and 6-31++G(d,p) basis set. The electronic parameters ΔEH-L were calculated by the following functionals: B3LYP, CAM-B3LYP, LC-wPBE, LC-BLYP, wB97X, M062X, M06HF, and M11 in addition to the second-order Møller-Plesset method (MP2) while always keeping the basis set mentioned before. An effect of basis set variation was studied by the optimal functional in combination with the following basis sets: 6-31G(d,p), 6-31++G(d,p), cc-pVDZ, AUG-cc-pVDZ, 6-311G(d,p), 6-311++G(d,p), cc-pVTZ, and AUG-cc-pVTZ. The NBO study was carried out with the M06HF/6-31++G(d,p) functional using the NBO method. The solvation parameters were calculated by M06HF/6-31++G(d,p) in the presence of the implicit solvation model Solvation Model based on Density (SMD). The excited states were calculated by M06HF/6-31++G(d,p) by the implicit solvation model Conductor Polarizable Continuum Model (CPCM).
RESUMO
The density functional theory method using the B3LYP/6-31G(d,p) level of theory was used to perform isoenergetic maps in order to determine the lower energy conformers of four disaccharides constituting alginic acids, which are based on ß-D-mannuronic (M) and α-L-guluronic acid (G), called MM, GG, MG, and GM. The preferred structures are combined to monovalent (Li+, Na+, and K+) cations and further fully optimized, and an isoenergetic map corresponding to the complex (MG2-, 2Na+) was performed. Then, the reactivity of MG complexes with mono- and bivalent cations was studied using the global nucleophilic index. The position selectivity was also predicted using the local nucleophilic indices. It was demonstrated that experimental trends of relative reactivity and regioselectivity of the complexes are correctly predicted using these empirical indices of reactivity. Graphical abstract MM, GG, MG, and GM alginic acid disaccharides and reactivity of the MG metallic complexes.
