ChemicalApplicationsofGroupTheoryVibrationalSpectroscopy.pptVIP

Chemical Applicationsof Group TheoryVibrational Spectroscopy Edward A. Mottel Department of Chemistry Rose-Hulman Institute of Technology Spectroscopy Vibrational bands 100-5000 cm-1 (1.2 -60 kJ·mol-1) the stretching and bending motions of the molecule. depend on the symmetry of the molecule. Infrared Spectroscopy Electric Dipole Infrared Spectroscopy Raman Spectroscopy Raman Spectroscopy Raman Spectroscopy Carbon Monoxide Character Table of C?v Carbon Monoxide Carbon Monoxide Character Table of C?v Carbon Dioxide Character Table of D?h Carbon Dioxide Character Table of D?h Vibrational Frequencies of CO2 Isotopic Substitution To identify specific bands in a spectra (i.e., which bands are responsible for symmetric or asymmetric stretching or bending) isotopic substitution is often required. If the substituted atom moves in a vibrational mode, then the band will shift. If the isotope is heavier, the band shifts to a lower frequency. Vibrational Frequencies of CO2 * * There are no restrictions on how a molecule can bend or stretch, but certain bands may not appear in a spectra because they are symmetry forbidden. ir light source sample cell reference cell ir detector Io Io Is Ir An infrared spectra occurs because of an absorption of infrared light. Infrared bands will occur if the motion changes the electric dipole of the molecule. m = e r - + 1 ? = (1.602 x 10-19 C)(1 x 10-10 m) = 4.803 x 10-18 esu·cm = 4.803 D Infrared bands will occur if the motion changes the electric dipole of the molecule. C O m = 0.1 D Repulsion of the negative dipole and the negative wave of the electric field results in the atoms moving together. Absorption of some of the energy from the electric field causes the dipole to get bigger and smaller. monochromatic light source sample cell visible photon counter (visible laser) scattered light A Raman spectra occurs because of a change in the frequency of scattered light. Raman bands will occur if the motion changes the polarizability of th