UVViselectronic spectroscopy BabeBolyai University紫外可见光谱电子宝贝Bolyai大学.pptVIP

UV-Vis spectroscopy Absorption and Emission Calculation of electronic spectra TD-DFT (time-dependent DFT) #P TD(nstates=5) B3LYP/6-31+G(d,p) Run this job on an optimized geometry of formaldehyde * Electronic absorption spectroscopy Absortpion spectroscopy Provide information about presence and absence of unsaturated functional groups Useful adjunct to IR Determination of concentration, especially in chromatography For structure proof, usually not critical data, but essential for further studies NMR, MS not good for purity Emission Absorption: A transition from a lower level to a higher level with transfer of energy from the radiation field to an absorber, atom, molecule, or solid. Emission: A transition from a higher level to a lower level with transfer of energy from the emitter to the radiation field. If no radiation is emitted, the transition from higher to lower energy levels is called nonradiative decay. Absorption /chem-ed/spec/spectros.html Frank-Condon Principle The nuclear motion (10-13 s) is negligible during the time required for an electronic excitation (10-16 s). Since the nuclei do not move during the excitation, the internuclear distances remain constant and “the most probable component of an electronic transition involves only the vertical transitions”. Absorption and emission pathways McGarvey and Gaillard, Basic Photochemistry at /grants/dpc/instruct/index2.htm  Origin of electronic spectra Absorptions of UV-vis photons by molecule results in electronic excitation of molecule with chromophore. chromophore Any group of atoms that absorbs light whether or not a color is thereby produced. The electronic transition involves promotion of electron from a electronic ground state to higher energy state, usually from a molecular orbital called HOMO to LUMO. Biological chromophores The peptide bonds and amino acids in proteins The p electrons of the peptide group are delocalized over the carbon, nitrogen, and oxygen atoms. The n-p* transiti