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

Journal Article · Thu Jul 01 00:00:00 EDT 2010 · Journal of Molecular Spectroscopy, 262(1):49-60

DOI:https://doi.org/10.1016/j.jms.2010.05.002· OSTI ID:982940

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

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 (v14), 900.908 cm-1 (v16), and 683.46 cm-1 (v17). 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 (v33) and 587.89 cm-1 (v35). 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.

• Research Organization: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
• Sponsoring Organization: USDOE
• DOE Contract Number: AC05-76RL01830
• OSTI ID: 982940
• Report Number(s): PNNL-SA-70785; 24824; KP1704020; TRN: US201014%%12
• Journal Information: Journal of Molecular Spectroscopy, 262(1):49-60, Vol. 262, Issue 1
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ROTATIONAL STATES
VIBRATIONAL STATES
GROUND STATES
INFRARED SPECTRA
ISOMERS
RAMAN SPECTRA
ORGANIC COMPOUNDS
DOUBLE BONDS
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
Environmental Molecular Sciences Laboratory