A reevaluation of the assignment of the vibrational fundamentals and the rotational analysis of bands in the high-resolution infrared spectra of trans- and cis-1,3,5-hexatriene

作者：Craig Norman C^*; Leyden Matthew C; Moore Michael C; Patchen Amie K; van den Heuvel Titus; Blake Thomas A; Masiello Tony; Sams Robert L

来源：Journal of Molecular Spectroscopy, 2010, 262(1): 49-60.

DOI：10.1016/j.jms.2010.05.002

• cis- and trans-1,3,5-Hexatriene
• Quantum chemical predictions of intensities and anharmonic frequencies for vibrational transitions
• Assignments of vibrational fundamentals
• High-resolution infrared spectra
• Analysis of rotational structure
• Rotational constants

Assignments of the vibrational fundamentals of cis- and trans-1,3,5-hexatriene are reevaluated with new infrared and Raman spectra and with quantum chemical predictions of intensities and anharmonic frequencies. The rotational structure is analyzed in the high-resolution (0.0013-0.0018 cm(-1)) infrared spectra of three C-type bands of the trans isomer and two C-type bands of the cis isomer. The bands for the trans isomer are at 1010.96 cm(-1) (v(14)), 900.908 cm(-1) (v(16)), and 683.46 cm(-1) (v(17)). Ground state (GS) rotational constants have been fitted to the combined ground state combination differences (GSCDs) for the three bands of the trans isomer. The bands for the cis isomer are at 907.70 cm(-1) (v(33)) and 587.89 cm(-1) (v(35)). GS rotational constants have been fitted to the combined GSCDs for the two bands of the cis isomer and compared with those obtained from microwave spectroscopy. Small inertial defects in the GSs confirm that both molecules are planar. Upper state rotational constants were fitted for all five bands.

• 出版日期2010-7