Phase shift cavity ring down and FT-NIR spectra of C[sbnd]H vibrational transitions and band strengths of ethyl acetate

Abstract

The vibrational overtone spectra (Δυ = 5, 6) of CH transitions of ethyl acetate (CH3COO–CH2CH3) have been obtained using the phase shift cavity ring down (PS-CRD) technique at 295 K. The CH stretch fundamental and overtone transitions (Δυ = 1- 4) have been obtained using a Fourier transform infrared and near infrared spectrophotometer. Local mode frequencies ωe and anharmonicities ωexe are reported for the CH (ip) (in plane), CH (op) (out of plane) bonds of the methyl group attached to the carbonyl (CO) side and for the methyl CH3 (primary) and methylene CH2 (secondary) CH bonds of the ethyl group bonded to the O atom. The study includes computer deconvolution of the total band at each level and a density functional theory (DFT) calculation of deuterated analogues of ethyl acetate to help with the assignment of all the non-equivalent CH bonds in the molecule. From the assigned Δυ = 6 peak wavenumber, isolated frequencies and CH bond lengths are obtained for the different CH bonds. Band strengths, oscillator strengths, and transition moments were obtained experimentally for all transitions. The importance of the assigned vibrational transitions and integrated intensities for future studies of laser and atmospheric vibrational overtone photochemistry is discussed.