Mg-Containing Zn3O3 Structures for Detection of CO2: A DFT Study on CHEM Effects of SERS and Electronic Properties.

Surface-enhanced Raman spectra (SERS) and electronic-structure-based properties are important tools for investigation of the molecular sensing ability of nanoparticles. The present computational study is intended to explore the sensing ability of Zn3O3 and Mg-containing Zn3O3 structures for CO2 molecules by CHEM effects of the SERS technique. Geometries of CO2-adsorbed Zn3O3, Zn2MgO3 (Mg as a substitutional impurity), and Zn3O3Mg (Mg as an interstitial impurity) structures are modeled using the B3LYP/6-31G(d,p) level of density functional theory. The Mg site of the Zn2MgO3 and Zn3O3Mg structures is preferential for the adsorption of CO2. The observed energy trends are supported by geometrical analysis, molecular orbital interactions, redshifts in CO2 vibrational modes, and topological properties. Raman activity enhancement of the CO2 symmetric vibrational mode is significant when the molecule is adsorbed at the Mg site of Zn3O3Mg. The observed Raman activity enhancement is supported by SERS spectra obtained from anharmonic calculations carried out on B3LYP/6-31G(d,p) geometries and substantiated by a larger change in the polarizability with energy corresponding to the symmetric vibrational mode of CO2. The TDDFT calculations, frequency-dependent polarizabilities, and charge transfer interactions show that Zn3O3Mg is a good substrate for sensing of CO2, with visible wavelengths, by resonance Raman effect. The trends with adsorption energy, Raman activity, and excited state properties are also substantiated by B3LYP/6-311+G(d,p) calculations.