LUMINESCENCE SPECTROSCOPY (11.0) Flashcards
optical method based on the measurement of photon by excited species
emission of radiation or luminescence
provide info. on composition and amount of luminescent species
spectrum/ intensity released radiation
4 features of luminescence (name)
- inherent sensitivity (LOD = 1-3 orders of magnitude smaller than absorption,pbb levels
- large linear conc. range
- better selectivity than absorption spectroscopy
- less widely applicable than absorption methods
It is a type of luminescence that excitation is brought about through absorption of photons or radiation
fluorescence and phosphorescence
It is a type of luminescence that excitation is brought about by chemical reaction, not by a radition source
chemiluminescence
Electronic transition involves no change in electric spin (s excited to s ground)
also short lived (10^-5 s)
Fluorescence
electronic transition involves a change in the electronic spin (from triple excited state to singlet ground state) longer lifetime (10-4 - 10 s or longer); significantly less probable event than singlet/singlet transition
phosphorescence
Fluorescence and absorption lines whose wavelength are identical
Resonance lines
shift to longer wavelength for fluorescence lines or bands conpared with the absorption wavelengths
stroke’s shift
rate of absorption
very rapid (10-14 to 10-15 s)
slower rate; lifetime of excited state is inversely related to molar absortivities (10-3 to 5)
Rate of fluorescence and phosphorescence
deactivation processes
favored route of ground state is one that minimize the lifetime of excited state (faster route); if deactivation by fluorescence is rapid with respect to radiationless processes emission is observed
radiationless path is faster, then fluorescence is absent or less intense
DIFFERENT DEACTIVATION PROCESSES (PIEVI)
Vibrational relaxation internal conversion external conversion intersystem crossing phosphorescence
- loss of excess vibrational energy through collision bet. excited species and molecule of solvent
- energy transfer and slight inrease in temp of solvent
- very efficient
VIBRATIONAL RELAXATION