Visible and Ultraviolet Spectroscopy - 建構中可见和紫外光谱-建構中.ppt

Molecular SpectroscopyVisible and Ultraviolet Spectroscopy －UV/VIS Spectroscopy－UV/VIS Spectrometer －Application for Quantitative Analysis Ultraviolet: 190~400nm Violet: ? 400 - 420 nm Indigo: ? 420 - 440 nm Blue: ? 440 - 490 nm Green: ? 490 - 570 nm Yellow: ? 570 - 585 nm Orange: ? 585 - 620 nm Red: ? 620 - 780 nm Internal Energy of Molecules Etotal=Etrans+Eelec+Evib+Erot+Enucl Eelec: electronic transitions (UV, X-ray) Evib: vibrational transitions (Infrared) Erot: rotational transitions (Microwave) Enucl: nucleus spin (nuclear magnetic resonance) or (MRI: magnetic resonance imaging) Electronic Spectroscopy Ultraviolet (UV) and visible (VIS) spectroscopy This is the earliest method of molecular spectroscopy. A phenomenon of interaction of molecules with ultraviolet and visible lights. Absorption of photon results in electronic transition of a molecule, and electrons are promoted from ground state to higher electronic states. UV and Visible Spectroscopy In structure determination : UV-VIS spectroscopy is used to detect the presence of chromophores like dienes, aromatics, polyenes, and conjugated ketones, etc. Electronic transitions There are three types of electronic transition which can be considered; Transitions involving p, s, and n electrons Transitions involving charge-transfer electrons Transitions involving d and f electrons Absorbing species containing p, s, and n electrons Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy. s ? s* Transitions An electron in a bonding s orbital is excited to the corresponding antibonding orbital. The energy required is large. For example, methane (which has only C-H bonds, and can only undergo s ? s* transitions) shows an absorbance maximum at 125 nm. Absorption maxima due to s ? s* transitions are not seen in typical UV-VIS spectra (200 - 700 nm) n ? s* Transitions Saturat