Understanding Fermi resonances behind the complex vibrational spectra of the methyl groups in simple alcohol, thiol, and their ethers

Vibrational spectra of the methyl groups in CH3SH, CH3SCH3, CH3OH, and CH3OCH3 monomers were measured to analyze their complex features as a result of bend/umbrella-stretch Fermi resonance. Multiple bands were recorded between 2800-3000 cm(-1) associated with the vibrations of the methyl groups in CH3OH, and CH3OCH3. On the other hand, the corresponding spectra of CH3SH and CH3SCH3 are relatively simpler with main peaks between 2900 to 3000 cm(-1). Theoretical ab initio anharmonic algorithm using six normal modes on a methyl group with potential energy surface at CCSD(T)-F12/aug-cc-pVTZ quality is able to account for all the experimentally observed features across these four species. In CH3SCH3 and CH3SH, all three C-H stretch fundamentals are above 2900 cm(-1), but the fundamental of umbrella mode is lower than 1350 cm(-1), thus only the overtone states of two bending modes are able to borrow sufficient intensities. In CH3OCH3 and CH3OH, umbrella modes have frequencies similar to the bending modes and the C-H stretch fundamentals are red-shifted to 2850-2950 cm(-1) leading to more complex vibrational features due to better energy-matching condition.

Automated summary

The vibrational spectra of methyl groups in different monomers were measured to analyze the complex features resulting from bend/umbrella-stretch Fermi resonance. CH3OH and CH3OCH3 exhibit more complex vibrational features compared to CH3SH and CH3SCH3, with multiple bands recorded and red-shifted C-H stretch fundamentals.