Publisher: American Chemical Society (ACS)

Issue: 6

License: {"URL"=>"http://pubs.acs.org/page/policy/authorchoice_ccby_termsofuse.html", "start"=>{"date-parts"=>[[2020, 2, 7]], "date-time"=>"2020-02-07T00:00:00Z", "timestamp"=>1581033600000}, "delay-in-days"=>0, "content-version"=>"vor"}

Publication date(s): 2020/02/18 (print) 2020/02/07 (online)

Pages: 2755-2765

Volume: 5 Issue: 6

Journal: ACS Omega

Link: {"URL"=>"http://pubs.acs.org/doi/pdf/10.1021/acsomega.9b03351", "content-type"=>"application/pdf", "content-version"=>"vor", "intended-application"=>"unspecified"} {"URL"=>"https://pubs.acs.org/doi/pdf/10.1021/acsomega.9b03351", "content-type"=>"unspecified", "content-version"=>"vor", "intended-application"=>"similarity-checking"}

URL: http://dx.doi.org/10.1021/acsomega.9b03351

How the methyl torsion transition energy in unsaturated systems is affected by its environment is investigated. It is strongly influenced by both its immediate neighborhood, (the number of methyl groups present in the molecule) and the intermolecular interactions. It is clear that the intermolecular interactions have a major influence on the torsion transition energy, as demonstrated unambiguously previously for mesitylene and also seen here for other systems. In part, this may be caused by the fact that the methyl torsion is rarely a pure mode (unless enforced by symmetry). Where the crystal structure is available, the assignments have been supported by CASTEP calculations of the unit cell. The agreement between the observed and calculated spectra is generally good, although not perfect, toluene being a case in point, and highlights just how demanding it is to obtain accurate transition energies for low energy modes. The disagreement between observed and calculated inelastic neutron scattering spectra for meta-xylene and 9,10 dimethylanthracene is so severe that it would suggest that there are additional phases to those presently known. Comparison between the full periodic calculations and those for the isolated molecule shows that intermolecular interactions raise the methyl torsion transition energy by at least 8% and in some cases by more than 50%. The presence of more than one methyl group in the molecule generally raises the average torsion energy from the <100 cm–1 seen for single methyl groups to 150–200 cm–1.