US EPA

5349159 

Journal Article 

Absolute fundamental and overtone OH and OD stretching intensities of alcohols 

Wallberg, J; Kjaergaard, HG 

2019 

1 

Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
ISSN: 1386-1425
EISSN: 1873-3557 

208 

315-324 

English 

30342341 

10.1016/j.saa.2018.09.046 

WOS:000449900700038 

Absolute intensities of the ΔvOH = 1 - 2 and ΔvOD = 1 - 3 transitions were determined for a range of alcohols (methanol, ethanol, 2-propanol, 1-propanol and tert-butanol) using conventional Fourier transform infrared (FTIR) spectroscopy. The intensities of the OH stretching transitions are stronger than the corresponding OD stretching transitions and become increasingly stronger with higher overtone transitions as expected from the reduced masses of the oscillators. Furthermore, accurate absolute intensities of the third and fourth OH stretching overtone transitions were determined using our newly constructed integrated cavity ring down (CRD) and FTIR spectrometer with experimental uncertainties generally less than 10%. The experiments were complemented by local mode calculations, with the potential energy surfaces and the dipole moment functions determined at the CCSD(T)/aug-cc-pVTZ level of theory. The calculated oscillator strengths of the ΔvOH = 4 - 5 transitions are within 25% of the experimental results.