Quantum Computational and Spectroscopic Investigation of 3-aminosalicylic Acid

Quantum chemical calculations of 3-aminosalicylic acid (3ASA) (monomer and dimer forms) have been performed using DFT and TD-DFT theories with B3LYP/6-311 G(d,p) functional level in the ground and excited states. Using TD-DFT with IEF-PCM model, the electronic spectra of 3ASA in solvents were computed and correlated with the experimental data. The theoretically calculated absorption and emission maxima of 3ASA (monomer) are observed in the range of 343 - 347 nm (S₀ → S₁ transition) and 429 - 448 nm (S₁ → S₀ transition), respectively. The natural bond orbital (NBO) analysis shows that charge transfer interaction contributes significantly to stabilize the molecular system. In the case of dimer, hydrogen bonding plays a dominant role in stabilizing the molecular framework. Additionally, the obtained nonlinear optical (NLO) properties: polarizability (13.86 × 10^-24 e.s.u for monomer and 29.46 × 10^-24 e.s.u. for dimer), first-order hyperpolarizability (4.21 × 10^-30 e.s.u for monomer and 0.18 × 10^-30 e.s.u for dimer) and second-order hyperpolarizability (7.44 × 10^-36 e.s.u. for monomer and 14.32 × 10^-36 e.s.u. for dimer) were found to be larger than those of standard organic compounds suggesting that 3ASA has a significant NLO character for optoelectronic applications. The NLO properties of dimer may differ from monomer due to dimerization. Further, the radiative lifetime, light harvesting efficiency and band gap energy were calculated, and proposed that 3ASA may be useful in photovoltaics and wide bandgap power devices. HIGHLIGHTS: • DFT and TD-DFT theories were employed to calculate structural and molecular properties of 3ASA (monomer and dimer) in ground and excited states. • HOMO-LUMO study shows monomer and dimer of 3ASA are good reactive. • NBO analysis reflects that charge transfer interactions stabilized the 3ASA molecule. • Electronic absorption/emission spectra in solvents calculated by IEF-PCM/TD-DFT method correlate with experimental results. • Calculated NLO parameters suggested that 3ASA is a potential candidate for NLO material.