Conformational stability from temperature dependent FT-IR spectra of liquid rare gas solutions, barriers to internal rotation, vibrational assignment, structural parameters and ab initio calculations for 3-bromopropene

The infrared spectra of 3-bromopropene (allyl bromide), CH2=CHCH2Br, dissol ved in liquid krypton (- 110 to - 155 degrees C) and liquid xenon (- 55 to - 10 degrees C) at concentrations of about 1 x 10(-2) M are reponed. The te mperature dependence of the infrared spectra of three conformer pairs in th e xenon solution has been used to obtain an enthalpy difference of 184 +/- 12 cm(-1) (2.20 +/- 0.14 kJ/mol) with the gauche conformer the more stable rotamer. Utilizing the asymmetric torsional fundamental of the ris conforme r at 133 cm(-1) along with two accompanying hot bands, the gauche fundament al at 99 cm(-1), the enthalpy difference of 184 cm(-1), and the gauche dihe dral angle (BrCCC) of 116.1 degrees, the potential function governing the c onformational interchange has been determined. The cis to gauche and gauche to gauche barriers have been determined to be 707 and 848 cm(-1) respectiv ely. The adjusted r(0) structural parameters have been obtained from the pr eviously reported rotational constants and ab initio predicted values. The conformational stability and infrared intensities, along with the vibration al frequencies and structural parameters have been obtained from ab initio calculations. These data are compared to the corresponding experimental qua ntities when appropriate. A complete vibrational assignment is proposed for the gauche conformer and most of the fundamentals have been assigned for t he cis conformer. The overall results are compared and contrasted to those for some similar molecules. (C) 2000 Elsevier Science B.V. All rights reser ved.