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For example, the absorption spectrum for ethane shows a σ → σ* transition at 135 nm and that of water a n → σ* transition at 167 nm with an extinction coefficient of 7,000. Benzene has three aromatic π → π* transitions; two E-bands at 180 and 200 nm and one B-band at 255 nm with extinction coefficients respectively 60,000, 8,000 and 215.
Internal conversion is a transition from a higher to a lower electronic state in a molecule or atom. [1] It is sometimes called "radiationless de-excitation", because no photons are emitted. It differs from intersystem crossing in that, while both are radiationless methods of de-excitation, the molecular spin state for internal conversion ...
This should not be confused with an excited state, which is a metastable electronic state containing a minimum in the potential energy, and may be short or long-lived. When a molecule is excited by means such as UV/VIS spectroscopy it can undergo a molecular electronic transition : if such a transition brings the molecule into a repulsive state ...
[4] [5] Reverse electron transitions for all these types of excited molecules are also possible to return to their ground states, which can be designated as σ* → σ, π* → π, or π* → n. A transition in an energy level of an electron in a molecule may be combined with a vibrational transition and called a vibronic transition.
In gas phase spectroscopy, the fine structure afforded by these factors can be discerned, but in solution-state spectroscopy, the differences in molecular micro environments further broaden the structure to give smooth bands. Electronic transition bands of molecules may be from tens to several hundred nanometers in breadth.
In electronic spectroscopy, constructing a Deslandres table is a useful method to assign vibronic transitions. In such a table, the frequencies of the lines seen in an electronic spectrum of a molecule are collected so that the differences in energy between adjacent columns or rows are all the same (within experimental error).
The wave function of a single electron is the product of a space-dependent wave function and a spin wave function. Spin is directional and can be said to have odd parity. It follows that transitions in which the spin "direction" changes are forbidden. In formal terms, only states with the same total spin quantum number are "spin-allowed". [5]
Vibronic spectroscopy is a branch of molecular spectroscopy concerned with vibronic transitions: the simultaneous changes in electronic and vibrational energy levels of a molecule due to the absorption or emission of a photon of the appropriate energy.