Electronic, nonlinear optical, UV-vis and NBO analysis of methyl methacrylate for optoelectronic and optical applications: DFT study and impact of conformation.

Using Density Functional Theory (DFT) and time-dependent DFT (TD-DFT), we studied a compound widely used in daily life, namely: Methyl Methacrylate (MMA) monomer in its two stable isomers, cis-MMA and trans-MMA. The impact of conformation on the optical and electronic properties of MMA was highlighted. Structural parameters and thermodynamic properties were also assessed, and allowed to discuss the stability and reactivity of this compound. In addition, analysis of optoelectronic and electronic properties, global reactivity descriptors, natural bond orbital (NBO), and hole and electron reorganization energies was performed. The absorption and fluorescence properties, as well as the linear and nonlinear optical (NLO) properties of MMA were also investigated. The findings show that MMA is an insulator due to its wide band gap of 6.20 eV. It also exhibits good optoelectronic properties with high average electric field values of about 5.90 × 10 Vm for cis-MMA and 5.42 × 10 Vm for trans-MMA and high electric displacement values of at least 14.65 × 10 cm for cis-MMA and 14.33 × 10 cm for trans-MMA, suggesting a potential use for the design of piezoelectric and pyroelectric materials. In addition, trans-MMA has a dielectric constant close to that of good insulators; while cis-MMA exhibits a dielectric behaviour close to that of polymeric substances. Further, these materials are thermodynamically stable in its two conformations, with a good reactivity which can lead to good ability of polymerization. The analysis of the UV-vis spectra revealed that both forms of MMA absorb and emit mainly in the UV and that the Stokes shift of MMA is low, reducing its potential use in devices such as solar cells. At NLO level, MMA isomers exhibit weak optical properties such as second- and third-order optical susceptibility and cannot suitable for second and third harmonic generation; however, the conformation enhances second-order NLO response by at least 2 times when moving from cis- to trans-MMA, whereas the third-order response is almost unaffected. In addition, the conformation also affects the electronic and optoelectronic properties of MMA.