Rotational barrier and thermodynamical parameters of furfural, thiofurfural, and selenofurfural in the gas and solution phases: theoretical study based on density functional theory method

This work aims to study the trans and cis conformers of furfural, thiofurfural and selenofurfural in the gas and solution phases. Assuming that there is equilibrium between these conformers, the transition state has also been investigated. All computations have been done using density functional theory method with B3LYP as the functional and 6-311 ++G(d,p) as the basis sets. The optimized molecular structures and related parameters of these conformers are reported. The infrared wavenumbers and Raman activities of these conformers are also reported with appropriate assignments. The energy differences between the trans and cis conformers, associated barriers and thermodynamical parameters have been derived from the computations. It is found that the structural parameters are not much different in the gas and solution phases. However, in the gas phase, the trans conformer is always more stable, but increasing the polarity of the solvent leads to the cis conformer becoming more stable. The rotational barrier is always larger than the energy difference and both of them increase when the solvent becomes more polar. Some of the results for furfural compare satisfactorily with literature and therefore the data from this work will be useful for thiofurfuraldehyde and selenofurfuraldehyde, as their literature is limited.