Jablonski diagram
Encyclopedia
A Jablonski diagram, named after the Polish physicist Aleksander Jabłoński, is a diagram that illustrates the electronic state
s of a molecule
and the transitions between them. The states are arranged vertically by energy and grouped horizontally by spin multiplicity
. Nonradiative transitions
are indicated by squiggly arrows and radiative transitions
by straight arrows. The vibrational ground states of each electronic state are indicated with thick lines, the higher vibrational states with thinner lines.
. Nonradiative transitions arise through several different mechanisms, all differently labeled in the diagram. Relaxation of the excited state to its lowest vibrational level is labeled vr
in the diagram. This process involves the dissipation of energy from the molecule to its surroundings, and thus it cannot occur for isolated molecules. A second type of nonradiative transition is internal conversion
(ic), which occurs when a vibrational state of an electronically excited state can couple to a vibrational state of a lower electronic state. A third type is intersystem crossing
(isc); this is a transition to a state with a different spin multiplicity. In molecules with large spin-orbit coupling
, intersystem crossing is much more important than in molecules that exhibit only small spin-orbit coupling. This type of nonradiative transition can give rise to phosphorescence
.
Electronic state
Electronic state is a quantum state of a system consisting of electrons . The state with lowest energy is called ground state, states with higher energy are excited states.See Energy level....
s of a molecule
Molecule
A molecule is an electrically neutral group of at least two atoms held together by covalent chemical bonds. Molecules are distinguished from ions by their electrical charge...
and the transitions between them. The states are arranged vertically by energy and grouped horizontally by spin multiplicity
Term symbol
In quantum mechanics, the Russell-Saunders term symbol is an abbreviated description of the angular momentum quantum numbers in a multi-electron atom. It is related with the energy level of a given electron configuration. LS coupling is assumed...
. Nonradiative transitions
Conical intersection
In quantum chemistry, a conical intersection of two potential energy surfaces of the same spatial and spin symmetries is the set of molecular geometry points where the two potential energy surfaces are degenerate . Conical intersections are ubiquitous in both trivial and non-trivial chemical...
are indicated by squiggly arrows and radiative transitions
Photoluminescence
Photoluminescence is a process in which a substance absorbs photons and then re-radiates photons. Quantum mechanically, this can be described as an excitation to a higher energy state and then a return to a lower energy state accompanied by the emission of a photon...
by straight arrows. The vibrational ground states of each electronic state are indicated with thick lines, the higher vibrational states with thinner lines.
Transitions
Radiative transitions involve the absorption, if the transition occurs to a higher energy level, or the emission, in the reverse case, of a photonPhoton
In physics, a photon is an elementary particle, the quantum of the electromagnetic interaction and the basic unit of light and all other forms of electromagnetic radiation. It is also the force carrier for the electromagnetic force...
. Nonradiative transitions arise through several different mechanisms, all differently labeled in the diagram. Relaxation of the excited state to its lowest vibrational level is labeled vr
Vibrational energy relaxation
Vibrational energy relaxation, or vibrational population relaxation, is a process in which the population distribution of molecules in quantum states of high energy level caused by an external perturbation returns to the Maxwell-Boltzmann distribution....
in the diagram. This process involves the dissipation of energy from the molecule to its surroundings, and thus it cannot occur for isolated molecules. A second type of nonradiative transition is internal conversion
Internal conversion (chemistry)
Internal conversion is a transition from a higher to a lower electronic state in a molecule or atom. It is sometimes called "radiationless de-excitation", because no photons are emitted...
(ic), which occurs when a vibrational state of an electronically excited state can couple to a vibrational state of a lower electronic state. A third type is intersystem crossing
Intersystem crossing
Intersystem crossing is a radiationless process involving a transition between two electronic states with different spin multiplicity.-Singlet and triplet states:...
(isc); this is a transition to a state with a different spin multiplicity. In molecules with large spin-orbit coupling
Angular momentum coupling
In quantum mechanics, the procedure of constructing eigenstates of total angular momentum out of eigenstates of separate angular momenta is called angular momentum coupling. For instance, the orbit and spin of a single particle can interact through spin-orbit interaction, in which case the...
, intersystem crossing is much more important than in molecules that exhibit only small spin-orbit coupling. This type of nonradiative transition can give rise to phosphorescence
Phosphorescence
Phosphorescence is a specific type of photoluminescence related to fluorescence. Unlike fluorescence, a phosphorescent material does not immediately re-emit the radiation it absorbs. The slower time scales of the re-emission are associated with "forbidden" energy state transitions in quantum...
.
External links
- Florida State University: Jablonski diagram primer
- University of Victoria: Jablonski diagram
- http://micro.magnet.fsu.edu/primer/java/jablonski/lightandcolor/
- http://docs.google.com/View?id=dfk4gz7_1tbc3vqhs
