PREDICTION OF DIPROPYL SULFONE PROPERTIES BY DENSITY FUNCTIONAL THEORY METHODS: CONFORMATIONAL ANALYSIS AND SIMULATED IR SPECTRUM

Abstract

In this work, the conformational and vibrational analysis of dipropyl sulfone in its isolated gaseous state with identification of all stable conformers, their energy and degeneracy, relative population determined by Boltzmann distribution, as well as IR spectra have been performed by density functional theory (DFT) methods. Several DFT methods and basis sets were tested. It was demonstrated that the various local and hybrid DFT functionals such as well-known B3LYP, regardless of the size of basis sets, completely fail in the prediction of correct molecular structures, let alone the IR spectra. It was found that only long-range corrected hybrid density functionals, combined with decently sized basis sets are capable to predict correct values of dihedral angles between non-bonded atomic groups: the most important coordinates in conformational analysis. Thus, wB97XD/6-311++G(2df,2pd) method/basis set combination appears to be the best method for the titled system both in terms of geometry and IR spectra prediction. A detailed analysis of the potential energy surface revealed the existence of 28 distinct conformers with various populations at 298 K, which have significant impact in the simulated IR spectra. The linear scaling equation (LSE) fitting methodology was successfully adopted for the calibration of wavenumbers and achievement of the best match between theoretical and experimental absorption regions of functional groups in sulfones. Moreover, in the construction of the simulated IR spectra, the Lorentzian broadening of each calculated mode with different full widths at half maximum was considered to obtain extinction coefficients, thus more realistic ε(ν) dependency, that is directly comparable with experimental spectra. The authenticity of the results obtained have been verified by comparison with existing experimental literature data on sulfones.