Comparative vibrational analysis of 1,2-Dinitro benzene and 1-Fluoro-3-nitro benzene: A combined experimental (FT-IR and FT-Raman) and theoretical study (DFT/B3LYP/B3PW91)

In this work, the comparative analysis is made on the structure and vibrational spectra of 1,2-Dinitro benzene (1,2-DNB) and 1-Fluoro-3-nitro benzene (1-F-3-NB) molecules. The FT-IR and FT-Raman experimental spectra of the molecules have been recorded using Bruker IFS 66 V spectrometer in the range of 4000–100 cm−1. Making use of the recorded data, the complete vibrational assignments are made and analyses of the observed fundamental bands of molecules are carried out. The experimental determinations of vibrational frequencies are compared with those obtained theoretically from ab-initio Hartree-fock (HF) and DFT (B3LYP and B3PW91) methods with 6-31++G (d, p) and 6-311++G (d, p) basis sets. The differences between the observed and scaled wave number values of most of the fundamentals of the molecules are very small in B3LYP than HF. The geometries and normal modes of vibrations obtained from ab-initio HF and B3LYP/B3PW91 calculations are compared with the experimentally observed data. Comparison of the simulated spectra of the molecules provides important information regarding the difference and similarity of the vibrational characteristics between the molecules. The impact of substitutions on the structures between the molecules is also investigated.

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► A comparative study is made on the structures of 1,2-Dinitro benzene and 1-Fluoro-3-nitro benzene.
► The HF/DFT (B3LYP&B3PW91) methods with 6-31++G (d, p) and 6-311++G (d, p) basis sets are used for comparison.
► The geometrical parameters are compared between 1,2-DNB and 1-F-3-NB with related molecules.
► The standard deviation (SD) calculation made between experimental and computed frequencies (HF/DFT) for both 1,2-DNB and 1-F-3-NB is presented.
► All the vibrational characteristics of the molecules are compared and the important information is observed.