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Introduction
Electronic transitions
When an atom or molecule absorbs energy, electrons are promoted from their
ground state to an excited state. In a molecule, the atoms can rotate and vibrate
with respect to each other. These vibrations and rotations also have discrete energy
levels, which can be considered as being packed on top of each electronic level.
Absorbing species containing p, s, and n electrons
s ® s* Transitions
n ® s* Transitions
Saturated compounds containing atoms with lone pairs (non-bonding electrons) are
capable of n ® s* transitions. These transitions usually need less energy than s ® s *
transitions. They can be initiated by light whose wavelength is in the range 150 -
250 nm. The number of organic functional groups with n ® s* peaks in the UV region
is small.
n ® p* and p ® p* Transitions
The solvent in which the absorbing species is dissolved also has an effect on the
spectrum of the species. Peaks resulting from n ® p* transitions are shifted to
shorter wavelengths (blue shift) with increasing solvent polarity. This arises from
increased solvation of the lone pair, which lowers the energy of the n orbital. Often
(but not always), the reverse (i.e. red shift) is seen for p ® p* transitions. This is
caused by attractive polarisation forces between the solvent and the absorber,
which lower the energy levels of both the excited and unexcited states. This effect
is greater for the excited state, and so the energy difference between the excited
and unexcited states is slightly reduced - resulting in a small red shift. This effect
also influences n ® p* transitions but is overshadowed by the blue shift resulting
from solvation of lone pairs.
Many inorganic species show charge-transfer absorption and are called charge-
transfer complexes. For a complex to demonstrate charge-transfer behaviour, one
of its components must have electron donating properties and another component
must be able to accept electrons. Absorption of radiation then involves the transfer
of an electron from the donor to an orbital associated with the acceptor.
Molar absorbtivities from charge-transfer absorption are large (greater that 10,000
L mol-1 cm-1).
Luminescence
Introduction
• Chemi-luminescence spectroscopy
Fluorescence and phosphorescence (photoluminescence)
The electronic states of most organic molecules can be divided into singlet states
and triplet states;
Fluorescence
Absorption of UV radiation by a molecule excites it from a vibrational level in the
electronic ground state to one of the many vibrational levels in the electronic
excited state. This excited state is usually the first excited singlet state. A molecule
in a high vibrational level of the excited state will quickly fall to the lowest
vibrational level of this state by losing energy to other molecules through collision.
The molecule will also partition the excess energy to other possible modes of
vibration and rotation. Fluorescence occurs when the molecule returns to the
electronic ground state, from the excited singlet state, by emission of a photon. If a
molecule which absorbs UV radiation does not fluoresce it means that it must have
lost its energy some other way. These processes are called radiationless transfer of
energy. Have a look at this diagram:
Phosphorescence
A molecule in the excited triplet state may not always use intersystem crossing to
return to the ground state. It could lose energy by emission of a photon. A
triplet/singlet transition is much less probable than a singlet/singlet transition. The
lifetime of the excited triplet state can be up to 10 seconds, in comparison with 10-5
s to 10-8 s average lifetime of an excited singlet state. Emission from triplet/singlet
transitions can continue after initial irradiation. Internal conversion and other
radiationless transfers of energy compete so successfully with phosphorescence
that it is usually seen only at low temperatures or in highly viscous media.
Chemi-luminescence
NO + O3 ® NO2* + O2