Gas-Phase Raman Spectra and the Potential Energy Function for the Internal Rotation of 1,3-Butadiene and Its Isotopologues

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2011-08, Vol.115 (32), p.8920-8927
• Main Authors: Boopalachandran, Praveenkumar, Craig, Norman, Groner, Peter, Laane, Jaan
• Format: Article
• Language: English
• Subjects: A: Kinetics, Spectroscopy; Band spectra; Bands; Constants; Mathematical models; Potential energy; Raman spectra; Spectra; Vibration
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp2051596

The gas-phase Raman spectra of 1,3-butadiene and its 2,3-d 2, 1,1,4,4-d 4, and -d 6 isotopologues have been recorded with high sensitivity in the region below 350 cm–1 in order to investigate the internal rotation (torsional) vibration. Based on more accurate structural information, the internal rotor constants Fn were calculated as a function of rotation angle (ϕ). The data for all the isotopologues were then fit using a one-dimensional potential energy function of the form V = 1/2∑Vn (1 – cos ϕ). Initial Vn values were based on those generated from theoretical calculations. The agreement between observed and calculated frequencies is very good, although bands not taken into account were present in the spectra. The energy difference between the trans and gauche forms was determined to be about 1030 cm–1 (2.94 kcal/mol), and the barrier between the two equivalent gauche forms was determined to be about 180 cm–1 (0.51 kcal/mol), which agrees well with high-level ab initio calculations. An alternative set of assignments also fits the data quite well for all of the isotopologues. For this model, the energy difference between the trans and gauche forms is about 1080 cm–1 (3.09 kcal/mol), and the barrier between gauche forms is about 405 cm–1 (1.16 kcal/mol).