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UV-Vis Lesson 1: Electronic

Transitions
UV-Vis spectra measure electronic transitions. The specific transitions which occur in UV-Vis
are in the energy domain of the ultraviolet or UV (200-400 nm) and visible or Vis (400 - 800
nm) ranges of the electromagnetic spectrum. The electronic transitions observed in the structures
we are concerned with arise from conjugated pi bond systems. In these systems UV-Vis light
energy promotes one electron from the highest-energy occupied bonding molecular orbital (the
HOMO orbital) into the lowest-energy unoccupied antibonding molecular orbital (the LUMO
orbital). When that electronic transition occurs, the pi bond character between two atoms is
sacrificed, but all of the sigma bond character is retained. After a certain amount of time, the
excited electron falls back down to the lower energy molecular orbital of the ground state pi
bond. By this means, compounds with pi bonds are detectable in a UV-Vis spectrum. These
intense electronic transitions are called π to π* transitions. During the excitation process, it is
possible to have rotation about the “double bond” and thus cis/trans isomerization often occurs.

There are two characteristics of a π to π* transition which are important. First, they occur only if
the molecule is irradiated with light energy of a particular wavelength, as measured in
nanometers (nm). The wavelength of the broad peak is measured at the point where the peak is
tallest. This nm value is known as a lambda maximum, abbreviated as λmax. The second notable
feature of an electronic transition is its intensity. Large or small, all peaks have a λmax. Usually
a UV-Vis spectrum has more than one peak. It is important to note that we are generally not
interested in the tallest peak. We are concerned with the λmax value associated with the π to π*
transition of the conjugated pi system.

Some of the π to π* peaks are so common that they are routinely overlooked. In this course,
most of the compounds that we will characterize by UV-Vis will be aromatic. All aromatic
compounds have an intense UV-Vis peak at about 205 nm. The presence of an intense peak at
205 nm indicates that the compound has an aromatic ring.

Consider a compound that has a reported λmax value of 294 nm. This means that the 294 nm λmax
value is characteristic of the compound and is related in a predictable manner to a structural
feature (chromophore) of the compound.
Optional Reading
Reading: The intensity of a UV-Vis peak depends upon a compound’s structure
and also upon the solvent, path length of the sample cell and the molar concentration of the
sample in the solution used to obtain the UV-Vis spectrum. Through the use of Beer’s law
a measure of the intensity, known as molar absorptivity, can be used to determine the
amount of sample in solutions of known substances. This is a common technique used by
analytical chemists and biochemists to quantify the amount of a known substance that is
present in a solution. We will not use Beer’s law in this class. But you should be cognizant
of Beer’s law and know that chemists, biochemists, and biologists apply Beer’s law to
quantitatively determine the amount of a known substance in a solution. You should look
up Beer's Law in your lecture text for more information.

QUVVis1-1. Which of the following does


UV-Vis measure?
(a) rotational barriers
(b) electronic transitions
(c) atomic masses
(d) isotopic distributions

QUVVis1-2. When a molecule absorbs AUVVis1-1.


UV-Vis energy, electrons undergo what (b) electronic transitions
type of transition?

QUVVis1-3. What structural feature gives AUVVis1-2.


rise to UV-Vis transitions that we will Electrons are promoted from a ground state
study in this course? HOMO to the LUMO, and generate an
excited state molecule.
QUVVis-4. What special name is given to AUVVis1-3.
this structural feature to identify its π bonds
importance in UV-Vis spectroscopy?

AUVVis1-4.
The pi bond systems that generate the
diagnostic UV-Vis peaks are identified as
chromophores.