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

Abstract

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 (βtot) 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 βtot 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 (β||) values are around 1474080.00 * 10-30 esu and 6,145,080.00 * 10-30 esu at 720nm 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 870nm. 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 (βtot) 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 βtot 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 (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.