Research on

Energy level diagram to show absorption of spectra include electronic ,

vibrational , rotational levels
Atomic & molecular spectra
Done by : Ibrahim ali ali el alfy
Biochemistry level 4
70021030
Supervised by Dr : magda akl
Rotationalvibrational spectroscopy is a branch of molecular spectroscopy
concerned with infrared and Raman spectra of molecules in the gas phase.
Transitions involving changes in both vibrational and rotational states can be
abbreviated as rovibrational (or ro-vibrational) transitions. When such
transitions emit or absorb photons (electromagnetic radiation), the frequency
is proportional to the difference in energy levels and can be detected by
certain kinds of spectroscopy. Since changes in rotational energy levels are
typically much smaller than changes in vibrational energy levels, changes in
It usually requires less energy to excite a vibrational mode than to excite an
electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

rotational state are said to give fine structure to the vibrational spectrum. For
a given vibrational transition, the same theoretical treatment as for pure
rotational spectroscopy gives the rotational quantum numbers, energy levels,
and selection rules. In linear and spherical top molecules, rotational lines are
found as simple progressions at both higher and lower frequencies relative to
the pure vibration frequency. In symmetric top molecules the transitions are
classified as parallel when the dipole moment change is parallel to the
principal axis of rotation, and perpendicular when the change is
perpendicular to that axis. The ro-vibrational spectrum of the asymmetric
rotor water is important because of the presence of water vapor in the
atmosphere.
For the present, it is sufficient to know that the electrons in an atom or
molecule have very specific energies--that is, the allowed electron energies
arequantized. This physical reality is reflected mathematically in the discrete
(integer or half-integer) values of the quantum numbers introduced above.
Recall that light is a propagating electromagnetic field. For the moment, we
can think of a photon as a localized spatial region with a rapidly fluctuating
electric field. If the electric field is oscillating with a frequency
(units of
cycles per second, or

), then the photon has energy

It usually requires less energy to excite a vibrational mode than to excite an

electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

where
is Planck's constant,
wavelength (in a vacuum).

is the speed of light, and

is the

As a photon approaches an atom or molecule, the electrons in the atom or

molecule begin to "feel" the photon's electric field. Let

be the energy of

an electron in one of the subshells, and let

be the higher energy of one of
the subshells that does not contain an electron. If the photon frequency
corresponds to the energy difference between these two energy levels, i.e., if

It usually requires less energy to excite a vibrational mode than to excite an

electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

then there is a chance that the electron will absorb the photon and use the
photon's energy to "jump" from its current subshell with energy

to the

vacant higher-energy subshell with energy

. The atom or
molecule is then said to be in an excited energy state. The time scale for this
absorption-excitation process is about
. This is the fundamental way
that matter absorbs light. If the photon frequency does not correspond to any
of the subshell energy differences, then the light cannot be absorbed and the
photon continues on its way.
illustrates three electron energy levels of a molecule. Which shells or
subshells these levels correspond to in a particular molecule is irrelevant for
the present discussion. The usual situation for a molecule is that the lowerenergy subshells are all occupied by electrons. It is then likely that visible
light will raise one of the outermost (highest energy) electrons to an
unoccupied energy level. (Raising an electron from the 1s shell to a higher
shell typically requires ultraviolet light.) The red and blue arrows in the left
panel of the figure represent electrons absorbing blue- and red-wavelength
photons and jumping from a low energy level to higher ones. The right panel
of the plot shows the corresponding absorption lines in the absorption
spectrum of the molecule.
It usually requires less energy to excite a vibrational mode than to excite an
electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

The probabilities for photon absorption are generally different for different
transitions. Thus some absorption lines will be "stronger" than others. This is
represented by a higher magnitude of the blue absorption line in the righthand plot. In emission--the reverse of absorption--a photon is emitted when
an electron falls from an excited state to an unoccupied lower energy level. In
that case, some emission lines will be "brighter" than others. The visual
nature of these emission lines was the origin of the spectroscopic labels of
"sharp", "principle," "diffuse," and "fine," which were later related to the
quantum numbers and orbitals as described above.

It usually requires less energy to excite a vibrational mode than to excite an

electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

This figure Illustration of three electron energy levels in a molecule and

absorption of blue and red light.
It usually requires less energy to excite a vibrational mode than to excite an
electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

the situation is typical of atoms and simple molecules in near isolation (e.g.,
in gases). However, the situation becomes more complicated for molecules
containing many atoms. In addition to the electron energy levels, molecules
also have vibrational modes . The blue spheres in the animations represent
atoms attached to the side of a larger molecule. These vibrational modes also
have quantized energy levels. That is, the molecules can vibrate only at
specific frequencies, which are determined by the molecule's structure and
the atoms involved.

It usually requires less energy to excite a vibrational mode than to excite an

electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.

It usually requires less energy to excite a vibrational mode than to excite an

electron from one subshell to another. The spacing between the quantized
vibrational energy levels is thus less than between electron orbitals. A quick
calculation is instructive. Molecular vibrational frequencies fall in the
to
range. For
,
gives a wavelength of
,
which is in the mid-infrared. Thus infrared light can excite a molecule from
one vibrational mode to another (with no change in the electronic energy
level). The corresponding vibrational energy difference is
. (A useful relation for these sorts of calculations
is
.)
Now suppose that we are interested in an electronic transition corresponding
to a blue wavelength of

. The corresponding electronic

energy shift is
. If the vibrational modes now
allow energy levels that are equal to the electronic transition
a vibrational
level, the energy shift can be
. The corresponding wavelengths
are then

, which in the current example

gives
and
, or a wavelength shift of 6 nm to either side of
the 440 nm electronic transition line.
The thin horizontal lines in the left panel of represent the additional molecular
energy levels when both electronic and vibrational levels are included in the
energy diagram. The thin blue and red arrows in the left panel illustrate how
the presence of vibrational modes allows for more possible electronic
transitions to occur in the wavelength neighborhoods of the electronic
transitions between subshells. These transitions add more spectral lines to
the absorption spectrum, as shown by the thin lines in the right-hand panel.