Excimer

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An excimer[1] (originally short for excited dimer) is a short-lived

dimeric or heterodimeric molecule formed from two species, at least
one of which is in an electronic excited state. Excimers are often
diatomic and are formed between two atoms or molecules that
would not bond if both were in the ground state. The lifetime of an
excimer is very short, on the order of nanoseconds. Binding of a
larger number of excited atoms form Rydberg matter clusters the
lifetime of which can exceed many seconds.

Contents
[hide]

• 1 Formation and
decay
• 2 Usage note
• 3 Examples and
use
• 4 References
• 5 See also
 • 6 External links

[edit] Formation and decay

Under the molecular orbital formalism, a typical ground-state

molecule has electrons in the lowest possible energy levels.
According to Hund's rule, at most two electrons can occupy a given
orbital, and if an orbital contains two electrons they must be in
opposite spin states. The highest occupied molecular orbital is
called the HOMO and the lowest unoccupied molecular orbital is
called the LUMO; the energy gap between these two states is known
as the HOMO/LUMO gap. If the molecule absorbs light whose energy
is larger than this gap, an electron in the HOMO may be excited to
the LUMO. This is called the molecule's excited state.

Excimers are only formed when one of the dimer components is in

the excited state. When the excimer returns to the ground state, its
components dissociate and often repel each other. The wavelength
of an excimer's emission is longer (smaller energy) than that of the
excited monomer's emission. An excimer can thus be measured by
fluorescent emissions.
Because excimer formation is dependent on a bimolecular
interaction, it is promoted by high monomer density. Low-density
conditions produce excited monomers that decay to the ground
state before they interact with an unexcited monomer to form an
excimer.

[edit] Usage note

The term excimer (excited state complex) is, strictly speaking,

limited to cases in which a true dimer is formed; that is, both
components of the dimer are the same molecule or atom. The term
exciplex refers to the heterodimeric case; however, common usage
expands excimer to cover this situation.

[edit] Examples and use

Heterodimeric diatomic complexes involving a noble gas and a

halide, such as xenon chloride, are common in the construction of
excimer lasers, which are excimers' most common application.
These lasers take advantage of the fact that excimer components
have attractive interactions in the excited state and repulsive
interactions in the ground state. The molecule pyrene is another
canonical example of an excimer that has found applications in
biophysics to evaluate the distance between biomolecules[2].

In organic chemistry many reactions occur through an exciplex for

example those of simple arene compounds with alkenes: [3] The
reactions of benzene and their products depicted are a
[2+2]cycloaddition to the ortho product (A) [4]., a [2+3]cycloaddition
to the meta product (B) [5] and the [2+4]cycloaddition to the para
product (C) [6] with simple alkenes such as the isomers of 2-butene.
In these reactions it is the arene that is excited.
As a general rule the regioselectivity is in favor of the ortho adduct
at the expense of the meta adduct when the amount of charge
transfer taking place in the exciplex increases.

[edit] References

1. ^ Birks, JB "Excimers", Rep. Prog. Phys. 1975, 38, 903-974.

2. ^ Conibear PB, Bagshaw CR, Fajer PG, Kovacs M, Malnasi-Csizmadia
A. (2003). Myosin cleft movement and its coupling to actomyosin
dissociation. Nat Struct Biol 10(10):831-5.
3. ^ Photochemistry of Arenes—Reloaded Jochen Mattay Angew.
Chem. Int. Ed. 2007, 46, 663 – 665 doi:10.1002/anie.200603337
4. ^ 1-cyanobicyclo[4.2.0]octa-2,4-dienes and their synthesis United
States Patent 2,805,242 Issue Date: September 3, 1957 Link
5. ^ A Photochemical 1,3 Cycloaddition of Olefins to Benzene K. E.
Wilzbach and Louis Kaplan J. Am. Chem. Soc.; 1966; 88(9) pp 2066 -
2067; doi:10.1021/ja00961a052
6. ^ Photoaddition of benzene to olefins. II. Stereospecific 1,2 and 1,4
cycloadditions Kenneth E. Wilzbach and Louis Kaplan J. Am. Chem.
Soc.; 1971; 93(8) pp 2073 - 2074; doi:10.1021/ja00737a052