ExamIIIstudyguide

SPECTROSCOPY:THEBIGPICTURE

Types of spectroscopic transitions include: absorption, spontaneous emission, stimulated emission.

In addition, photons can also be scattered from molecules (Raman spectroscopy).
The likelihood of a transition occurring is proportional to the transition dipole moment. This has to be
nonzero for a transition to be allowed. If the transition dipole moment is zero, the transition is said to be
forbidden.
Electronic transitions generally occur in the visible and UV regions of the electromagnetic spectrum.
Vibrational transitions generally occur in the infrared region.
Rotational transitions generally occur in the microwave region.
The corresponding quantum numbers are: n (electronic), v (vibrational), and J (rotational). You should know
the allowed ranges for each.
ROTATIONALSPECTROSCOPY

The gross selection rule says that a molecule must have a permanent dipole moment in order to observe a
rotational transition.
The specific selection rule is J = 1 and M = 0, 1.
The spacing between rotational energy levels is not uniform, but the spacing between rotational transitions is
uniform (in the rigid rotor approximation).
Centrifugal distortion causes deviations from the rigid rotor model. However, this tends to be quite small.
INFRAREDSPECTROSCOPY

The gross selection rule says there must be a change in dipole moment during the transition for the transition
to be allowed.
The quantum selection rule is v = 1. This is based on the harmonic oscillator approximation.
The spacing between vibrational energy levels is uniform.
Anharmonicity accounts for deviations from the harmonic oscillator model.
An anharmonic potential can be approximated by a Morse potential (if you need this equation, Ill provide it).
Transitions that are forbidden in the harmonic oscillator approximation (e.g., overtones) become weakly
allowed when the system behaves anharmonically. These tend to be much weaker than the allowed transitions
predicted by the harmonic oscillator.
In the anharmonic model, the energy spacing is no longer uniform. Because of this, overtones are not exactly
equal to integer multiples of the fundamental transition.
Linear molecules (diatomics and linear polyatomics) have 3N 5 vibrational degrees of freedom. These are
called normal modes.
Nonlinear molecules have 3N 6 normal modes.
Normal modes can combine to form so-called combination bands where a single photon simultaneously
excites multiple normal modes.
ROTATIONALVIBRATIONALSPECTROSCOPY

Transitions between rotational levels of different vibrational levels give rise to rotational-vibrational (rovibrational) transitions.
The selection rules for these transitions (using the harmonic oscillator and rigid rotor models) is v = 1 and
J = 1.
When J = +1, these transitions are referred to as the R-branch of the ro-vibrational spectrum.
When J = -1, these transitions are referred to as the P-branch of the ro-vibrational spectrum.
RAMANSPECTROSCOPY

Raman spectroscopy is a type of vibrational spectroscopy.

 Using a classical analogy, a photon scatters off of a molecule. When it does so, it can exchange energy with
the molecule.
When the scattered photon does not exchange energy with the molecule, we call this Rayleigh scattering.
Hence, Rayleigh scattering is seen at the frequency of the incident photon.
Stokes scattering occurs when the photon loses energy (by giving it to the molecule). Accordingly, Stokes
scattering is observed at lower frequencies than the incident photon.
Anti-Stokes scattering occurs when the photon gains energy (the molecule loses energy). Accordingly, antiStokes scattering is observed at higher frequencies than the incident photon.
Rayleigh scattering accounts for the majority of the scattered photons (i.e., the Rayleigh line will be most
intense).
Stokes transitions tend to be more intense than anti-Stokes transitions because they arise from interactions
with molecules in the ground vibrational state. (Remember, upper vibrational states are sparsely populated at
normal temperatures.)
The gross selection rule says that the polarizability of the molecule must change during the transition and the
specific selection rule is v = 1.
ROTATIONALRAMANSPECTROSCOPY

Just like ro-vibrational spectroscopy, these involve transitions between rotational levels of different
vibrational levels. However, the selection rules are different: J = 0, 2.
When J = +2, these transitions are referred to as the S-branch of the rotational Raman spectrum.
When J = -2, these transitions are referred to as the O-branch of the rotational Raman spectrum.
When J = 0, these transitions are referred to as the Q-branch of the rotational Raman spectrum.
The S-branch transitions (J = +2) occur at lower energy and the O-branch transitions (J = -2) occur at
higher energy. Note that this is different than ro-vibrational spectroscopy where transitions corresponding to
J = +1 occur at higher energy and those corresponding to J = -1 occur at lower energy.
Note that rotational-Raman spectroscopy allows us to look at pure rotational transitions in molecules that
would otherwise not have a pure rotational spectrum.
LINEWIDTHS

Spectral lines are not infinitely narrowthey will always have some finite width.
There are two main contributions to this: (1) Doppler broadening and (2) Uncertainty broadening (also called
collisional or lifetime broadening).
ELECTRONICSPECTROSCOPY

In electronic spectroscopy, transitions can occur between vibrational levels of two different electronic states.
These are called vibronic transitions.
We showed that the transition dipole moment (an indicator of the likelihood of a transition) was proportional
to the Franck-Condon factor.
The Franck-Condon factor is an integral that represents the overlap between two vibrational wavefunctions of
different electronic states.
This overlap is greatest (and the corresponding transition is most intense) when the nuclear configuration of
the electronic excited state most closely resembles the configuration of the electronic ground state.
Because nuclear rearrangement is slow compared to electronic transitions, the electronic transition will occur
much faster than the nuclei can rearrange.
The 0-0 transitions for fluorescence and absorption will not coincide exactly.
All of the possible processes involving electronic spectroscopy can be represented on a Jablonski diagram.
These processes include: absorption, fluorescence, internal conversion, inter-system crossing, and
phosphorescence.