Molecular structure, vinyl rotation barrier, and vibrational dynamics of 2,6-dichlorostyrene. A theoretical and experimental research.
The molecular structure of 2,6-dichlorostyrene has been analyzed at MP2 and DFT levels using different basis sets concluding in a nonplanar geometry. The influence of either the level of theory or the nature of the substituent has been assessed. The vinyl-phenyl torsion barrier has also been investigated as a function of level of theory. The ultimate factors responsible for the torsion barrier have been studied using two different partitioning schemes, i.e., the total electronic potential energy and the natural bond orbital, NBO. A topological analysis of the electron density within the atom-in-molecule, AIM, theory predicts soft intramolecular chlorine (ring)-hydrogen (vinyl) contacts when the system becomes planar. A first complete vibrational study has been performed using theoretical data and experimental vibrational frequencies from IR, Raman and, for the first time, inelastic neutron scattering, INS, spectra. The new assignment proposed is based on a scaled quantum mechanical, SQM, force field and the wavenumber linear scaling, WLS, approach.
Ceacero-Vega
Antonio A
AA
Department of Physical and Analytical Chemistry, University of Jaén, Campus Las Lagunillas E23071 Jaén, Spain.
Ruiz
Tomas Peña
TP
Gómez
Manuel Fernández
MF
Roldán
José M Granadino
JM
Navarro
Amparo
A
Fernández-Liencres
M Paz
MP
Jayasooriya
Upali A
UA
D008956:Models, Chemical; D008958:Models, Molecular; D015394:Molecular Structure; D011789:Quantum Theory; D012399:Rotation; D013055:Spectrophotometry, Infrared; D013059:Spectrum Analysis, Raman; D013343:Styrenes / Q000737:chemistry*; D014732:Vibration; D014753:Vinyl Compounds / Q000737:chemistry*
D013343:Styrenes; D014753:Vinyl Compounds; C422705:2,6-dichlorostyrene