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

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_av) 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⁺–NH₃ and Na⁺–NH₃ groups are acceptor groups and a bridge composed by the three remaining NH₃ 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. [ABSTRACT FROM AUTHOR]