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The absorbance of a solution increases as attenuation of the beam increases. Absorbance is directly proportional to the path length, b, and the concentration, c, of the absorbing species. Beer's Law states that A = ebc, where e is a constant of proportionality, called the absorbtivity. Different molecules absorb radiation of different wavelengths. An absorption spectrum will show a number of absorption bands corresponding to structural groups within the molecule. For example, the absorption that is observed in the UV region for the carbonyl group in acetone is of the same wavelength as the absorption from the carbonyl group in diethyl ketone. Electronic transitions The absorption of UV or visible radiation corresponds to the excitation of outer electrons. There are three types of electronic transition which can be considered; 1. Transitions involving p, s, and n electrons 2. Transitions involving charge-transfer electrons 3. Transitions involving d and f electrons (not covered in this Unit) 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 Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain functional groups (chromophores) that contain valence electrons of low excitation energy. The spectrum of a molecule containing these chromophores is complex. This is because the superposition of rotational and vibrational transitions on the electronic transitions gives a combination of overlapping lines. This appears as a continuous absorption band. Possible electronic transitions of p, s, and n electrons are;
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 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 Most absorption spectroscopy of organic compounds is based on transitions of n or p electrons to the p* excited state. This is because the absorption peaks for these transitions fall in an experimentally convenient region of the spectrum (200 - 700 nm). These transitions need an unsaturated group in the molecule to provide the p electrons.
Molar absorbtivities from n ® p* transitions are relatively low, and range from 10 to100 L mol-1 cm-1 . p ® p* transitions normally give molar absorbtivities between 1000 and 10,000 L mol-1 cm-1 . 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. Charge - Transfer Absorption Many inorganic species show charge-transfer absorption and are called chargetransfer 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).
Introduction Luminescence is the emission of light by a substance. It occurs when an electron returns to the electronic ground state from an excited state and loses it's excess energy as a photon. Luminescence spectroscopy is a collective name given to three related spectroscopic techniques. They are;
• • •
Molecular fluorescence spectroscopy Molecular phosphorescence spectroscopy Chemi-luminescence spectroscopy
Fluorescence and phosphorescence (photoluminescence) The electronic states of most organic molecules can be divided into singlet states and triplet states;
Singlet state: All electrons in the molecule are spin-paired Triplet state: One set of electron spins is unpaired
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: Possible physical process following absorption of a photon by a molecule
Intra-molecular redistribution of energy between possible electronic and vibrational states The molecule returns to the electronic ground state.The excess energy is converted
to vibrational energy (internal conversion), and so the molecule is placed in an extremely high vibrational level of the electronic ground state. This excess vibrational energy is lost by collision with other molecules (vibrational relaxation). The conversion of electronic energy to vibrational energy is helped if the molecule is "loose and floppy", because it can reorient itself in ways which aid the internal transfer of energy. A combination of intra- and inter-molecular energy redistribution The spin of an excited electron can be reversed, leaving the molecule in an excited triplet state; this is called intersystem crossing. The triplet state is of a lower electronic energy than the excited singlet state. The probability of this happening is increased if the vibrational levels of these two states overlap. For example, the lowest singlet vibrational level can overlap one of the higher vibrational levels of the triplet state. A molecule in a high vibrational level of the excited triplet state can lose energy in collision with solvent molecules, leaving it at the lowest vibrational level of the triplet state. It can then undergo a second intersystem crossing to a high vibrational level of the electronic ground state. Finally, the molecule returns to the lowest vibrational level of the electronic ground state by vibrational relaxation. 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 Chemi-luminescence occurs when a chemical reaction produces an electronically excited species which emits a photon in order to reach the ground state. These sort of reactions can be encountered in biological systems; the effect is then known as bioluminescence. The number of chemical reactions which produce chemiluminescence is small. However, some of the compounds which do react to produce this phenomenon are environmentally significant. A good example of chemiluminescence is the determination of nitric oxide: NO + O3 ® NO2* + O2 NO2* ® NO2 + hv (l = 600 - 2800 nm)
The following graph shows the spectral distribution of radiation emitted by the above reaction:
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