화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.108, No.30, 6286-6293, 2004
Ab initio study of the torsional spectrum of glycolaldehyde
The torsional spectrum of glycolaldehyde (COH-CH2OH) is predicted from MP4(SDTQ)/cc-pVQZ ab initio calculations. This monosaccharide of astrophysical interest shows two large amplitude vibrations that confer nonrigid properties: the central bond torsion and the OH torsion. It presents five stable conformers, three of C-s symmetry (I-cis, II-trans, and IV-cis) and a double minimum of C-1 symmetry (III-trans and III'-trans). The favorite geometry, I-cis, stabilizes by the formation of a hydrogen bond connecting the eclipsed oxygen atoms. The relative energies of the secondary minima are 1278.2 (II-trans), 1297.2 (III and III'-trans) and 1865.2 cm(-1) (IV-cis). A barrier of 1895 cm(-1) hinders the cis --> trans interconversion. The barriers for the OH torsion are 2040 (cis) and 191 and 713 cm-1 (trans). The torsional energy levels have been calculated variationally up to J = 6 using a flexible model in two dimensions. Far-infrared frequencies and intensities have been determined at room temperature. In addition, the rotational parameters of the I-cis conformer have been computed to be A = 18583.85 MHz, B = 6563.83 MHz, C = 5009.34 MHz, D-J = -20.18 kHz, D-JK = -82.36 kHz, and D-K = 138.38 kHz at the zero vibrational level. The parameters corresponding to the trans form are A = 38019.19 MHz, B = 4406.79 MHz, C = 4076.73 MHz, and D-J = -109.28 kHz.