TY - JOUR
T1 - Absolute fundamental and overtone OH and OD stretching intensities of alcohols
AU - Wallberg, Jens
AU - Kjaergaard, Henrik G.
PY - 2019/2/5
Y1 - 2019/2/5
N2 - 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.
AB - 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.
U2 - 10.1016/j.saa.2018.09.046
DO - 10.1016/j.saa.2018.09.046
M3 - Journal article
C2 - 30342341
SN - 1386-1425
VL - 208
SP - 315
EP - 324
JO - Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
JF - Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy
ER -