Theoretical study of the Tetraaminelithium and Tetraaminesodium molecules complexed with H−, Li− and Na− anions: static and dynamic NLO parameters

• Published in: Journal of molecular modeling 2024-01, Vol.30 (1), p.8-8, Article 8
• Main Authors: Bekri, Lahcène, Elhorri, Abdelkader M., Hedidi, Madani, Zouaoui–Rabah, Mourad
• Format: Article
• Language: English
• Subjects: Ammonia; Anions; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Molecular Medicine; Original Paper; Oscillator strengths; Second harmonic generation; Solvation; Theoretical and Computational Chemistry; Wavelengths
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-023-05801-3

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 ( β tot ) 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 β tot equal to 563.20 and 691.99 * 10 −30 esu respectively and static second hyperpolarizabilities ( γ a v ) of 680.02 and 779.05 * 10 −35 esu. The highest dynamic first hyperpolarizabilities ( β || ) 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 + –NH 3 and Na + –NH 3 groups are acceptor groups and a bridge composed by the three remaining NH 3 ligands. The maximum wavelengths ( λ max ) 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 ( β tot ) 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 β tot 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 ( β || ) 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 ( ΔG solv ) were calculated using the implicit SMD model. Maximum wavelengths ( λ max ) and oscillator strengths ( f os ) were calculated by TD–CAM–B3LYP/6–31 +  + G(d,p) in the presence of the implicit CPCM model. Graphical abstract