Transition dipole moment

The Transition dipole moment or Transition moment, usually denoted for a

transition between an initial state, , and a final state, , is the electric dipole moment
associated with the transition between the two states. In general the transition dipole
moment is a complex vector quantity that includes the phase factors associated with the
two states. Its direction gives the polarization of the transition, which determines how the
system will interact with an electromagnetic wave of a given polarization, while the
square of the magnitude gives the strength of the interaction due to the distribution of
charge within the system. The SI unit of the transition dipole moment is the Coulomb
meter (Cm); a more conveniently sized unit is the Debye (D).

Definition

The transition dipole moment for the transition is given by the relevant off-
diagonal element of the dipole matrix, which can be calculated from an integral taken
over the product of the wavefunctions of the initial and final states of the transition, and
the dipole moment operator,

where the summations are over the positions of the electrons in the system. Giving the
transition dipole moment:

where the integral is, in principle over all space, but can be restricted to the region in
which the initial and final state wave functions are non-negligible.

Analogy with a classical dipole

A basic, phenomenological understanding of the transition dipole moment can be

obtained by analogy with a classical dipole. While the comparison can be very useful,
care must be taken to ensure that one does not fall into the trap of assuming they are the
same.

In the case of two classical point charges, and , with a displacement vector, ,
pointing from the negative charge to the positive charge, the electric dipole moment is
given by

In the presence of an electric field, such as that due to an electromagnetic wave, the two
charges will experience a force in opposite directions, leading to a net torque on the
dipole. The magnitude of the torque is proportional to both the magnitude of the charges
and the separation between them, and varies with the relative angles of the field and the
dipole:

Similarly, the coupling between an electromagnetic wave and an atomic transition with
transition dipole moment , depends on the charge distribution within the atom, the
strength of the electric field, and the relative polarizations of the field and the transition.
In addition, the transition dipole moment depends on the geometries and relative phases
of the initial and final states.

Origin

When an atom or molecule interacts with an electromagnetic wave of frequency , it can

undergo a transition to a higher energy state by absorbing a photon or a lower energy
state by emitting a photon, provided that the energy difference between the initial and
final states is the same as the photon energy . The presence of the electromagnetic
field can induce an oscillating electric dipole moment, referred to as the transition dipole
moment. If the charge, , is omitted one obtains as used in oscillator strength.

Applications

The transition dipole moment is useful for determining if transitions are allowed under
the electric dipole interaction. For example, the transition from a bonding orbital to an
antibonding orbital is allowed because the integral defining the transition dipole moment
is nonzero. Such a transition occurs between an even and an odd orbital; the dipole
operator is an odd function of , hence the integrand is an even function. The integral of
an odd function over symmetric limits returns a value of zero, while for an even function
this is not necessarily the case. This result is reflected in the parity selection rule for
electric dipole transitions.