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Electronic
Spectroscopy
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π2πΈππ 2 = πππππ ππππ π‘πππ‘
ππ = 12πΰΆ¨πΎπ
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Β· UV-Vis Terminology
β Chromophore: a UV-Visible absorbing functional group
β Bathochromic shift (red shift): to longer wavelengths
β Auxochrome: a substituent on a chromophore that causes a red shift
β Hypsochromic shift (blue shift): to shorter wavelengths
β Hyperchromic shift: to greater absorbanceβ Hypochromic shift: to lesser absorbance
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Β· Classes of Electron transitions
(1) , and n electrons (mostly organics)
(2) d and f electrons (inorganics/organometallics)
(3) charge-transfer (CT) electrons
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* and * transitions: high-energy, accessible in vacuum UV (max <150 nm). Not usually observed in molecular UV-Vis.
n * and * transitions: non-bonding electrons (lone pairs), wavelength (max) in the 150-250 nm region.
n * and * transitions: most common transitions observed in organic molecular UV-Vis, observed in compounds with lone pairs and multiple bonds with max = 200-600 nm.
Β· Charge transfer (CT)
β MLCT (metal-to-ligand charge transfer)β LMCT (ligand-to-metal charge transfer)
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