Matrix isolation FT-IR, FT-Raman spectroscopy, conformational ab initio calculations, and vibrational frequencies of meso and racemic-2,4-pentanediol

• DOI: 10.1016/j.molstruc.2003.09.023
• Publication Date: 2003-12-30T12:00:24Z
• Authors: Carlos E Manzanares; Dovie Reynolds; Ernest K Lewis; Craig J Moehnke; Nairmen Mina-Camilde; Mary C Salazar; Antonio J Hernandez
• Keywords: Conformational isomerism; Matrix Isolation; Racemic mixture

Abstract The infrared spectra of meso-2,4-pentanediol and racemic-2,4-pentanediol were measured in an argon matrix at 20 K. The Raman spectra of the pure liquids (meso and racemic) were measured at room temperature. The spectra were obtained using a Fourier transform spectrophotometer and a cryostat for the low temperature matrix. The meso and racemic forms of the diol were separated by means of a spinning band distillation column. The energies of nine possible conformers of the meso form and nine conformers of the racemic form were calculated. Extensive ab initio calculations using B3LYP, MP2 and HF methods with several basis sets consistently gave the lowest energy for the TT conformer of the meso form and the G − T (= TG − ) conformer of the racemic form. Ab initio calculations at the B3LYP/6-31G** level were performed for the lowest energy conformer of meso and racemic pentanediol to obtain the equilibrium geometry, vibrational frequencies, and infrared and Raman intensities. Calculated and experimental frequencies were compared to make vibrational assignments.