Rotational analysis of bands in the high-resolution infrared spectra of the three species of butadiene-1,4-d2;: refinement of the assignments of the vibrational fundamentals

Samples of trans,trans and cis,cis forms of butadiene-1,4-d(2) have been synthesized and found to contain useful amounts of the cis,trans species as a contaminant. Assignments of fundamental frequencies for the three isotoporners of butadiene-1,4-d(2) have been extended and improved from investigations of their Raman spectra as well as their infrared (IR) spectra. High-resolution IR spectra have been recorded for the three isotopomers, and a rotational analysis has been completed for strong bands of each species. Ground state and some upper state rotational constants have been fit. Corresponding ground state moments of inertia compare favorably with equilibrium moments of inertia obtained from B3LYP/6-311 ++G** theory. Two C-13 isotopomers are being prepared, and an improved structural analysis of butadiene will soon be available to assess how pi-electron delocalization affects its structure. (C) 2004 Elsevier Inc. All rights reserved.