Abstract

The crystallization of oxyquinolinium 3-carboxypropanoate (OXSU) was successfully achieved using a well-optimized slow evaporation approach. Although earlier experimental investigations have discussed its structural, thermal, and nonlinear optical (NLO) characteristics, the present study is a detailed computational analysis to clarify the electronic basis of its NLO response. X-ray diffraction (XRD) studies established the non-centrosymmetric (NCS) P21 crystal structure of OXSU, fulfilling the fundamental symmetry condition for second-order NLO activity. Hirshfeld surface (HS) analysis indicated that the intermolecular O–H…O/N–H…O hydrogen-bonding interactions were particularly important for stabilizing the acentric packing of OXSU for SHG activity. Vibrational spectroscopy (FTIR and FT-Raman) also provided evidence of both functional groups and hydrogen bonding interactions. Moreover, Mulliken charge analysis revealed evidence of charge redistribution during the formation of an asymmetrical charge density. Frontier molecular orbital (FMO) energy level calculations indicated an energy gap (ΔE = 3.82 eV) that encouraged intramolecular charge transfer (ICT). The molecular electrostatic potential (MEP) indicated regions of nucleophilic and electrophilic directions suggesting asymmetrical electron mobility. The material exhibits a high first hyperpolarizability (β = 16.94 × 10-30 esu), which is 33 times that of urea. The second harmonic generation (SHG) response is 30 % greater compared to potassium dihydrogen phosphate (KDP) and demonstrate phase-matchable behavior. This study documents the structure-property (SP) relationships in OXSU, correlating its acentric crystalline packing, hydrogen bonding interactions and charge transfer characteristics with NLO performance. These results establish that OXSU is a highly efficient, phase matchable organic NLO material with significant potential for optoelectronic applications.

Keywords

Organic NLO Single Crystal, Density Functional Theory, Hirshfeld Surface Analysis, Vibrational Studies, Optical Material, Phase Matchable Material,

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