Improved force field of (E)-1,3,5-hexatriene based on deuteriated derivatives

Raman and IR spectra of ground-state (E)-1,3,5-hexatriene-3,4-d2 (d34EHT), (E)-1,3,5-hexatriene-3-d (d3EHT), (E)-1,3,5-hexatriene-1,1-d2 (d11EHT), and (E)-1,3,5-hexatriene-2,5-d2 (d25EHT) are reported. Together with previously published spectra of (E)-1,3,5-hexatriene (EHT), these spectra are used to refine a scaled ab initio force field from the literature, calculated at the HF/6-31G level, and the spectra of EHT, d34EHT, d3EHT, d11EHT, and d25EHT are interpreted by use of the resulting refined force field. The changes in the force field are discussed, as are the changes in normal modes upon deuteriation.