Vibrational spectra, ab initio/DFT electronic structure calculations, and normal coordinate analysis of 2-bromo-5-fluorobenzaldehyde

Abstract

FT-IR (4000–400 cm −1) and FT-Raman (3500–50 cm −1) spectral measurements of solid samples of 2-bromo-5-fluorobenzaldehyde (BFB) have been done. Ab initio (RHF/6-311G*) and DFT (B3LY/6-311G* and B3PW91/6-311G*) calculations have been performed giving energies, optimized structures, harmonic vibrational frequencies, depolarization ratios, infrared intensities, Raman activities and atomic displacements. Furthermore force field calculations have been performed by normal coordinate analysis. Force field calculations showed that several normal modes are mixed in terms of the internal coordinates. A complete assignment of the observed spectra, based on spectral correlations, electronic structure and normal coordinate analysis, has been proposed. Optimization leads to C S symmetry with O- trans and O- cis isomers, with respect to aldehydic oxygen and bromine, with O- trans-isomer as the low energy stable form. The energy difference between the two isomers is 2.95084 kcal/mol. The results of the calculations have been used to simulate IR and Raman spectra for BFB that showed excellent agreement with the observed spectra. The SQM method, which implies multiple scaling of the ab initio and DFT force fields has been shown superior to the uniform scaling approach.