Transition dipole moment

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Three wavefunction solutions to the time-dependent Schr�dinger equation for an

electron in a harmonic oscillator potential. Left: The real part (blue) and
imaginary part (red) of the wavefunction. Right: The probability of finding the
particle at a certain position. The top row is an energy eigenstate with low
energy, the middle row is an energy eigenstate with higher energy, and the bottom
is a quantum superposition mixing those two states. The bottom-right shows that the
electron is moving back and forth in the superposition state. This motion causes an
oscillating electric dipole moment, which in turn is proportional to the transition
dipole moment between the two eigenstates.
The transition dipole moment or transition moment, usually denoted
{\displaystyle \scriptstyle {\mathbf {d} _{nm}}} \scriptstyle {{\mathbf
{d}}_{{nm}}} for a transition between an initial state, {\displaystyle \scriptstyle
{m}} \scriptstyle{m}, and a final state, {\displaystyle \scriptstyle {n}}
\scriptstyle {n}, 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).

Contents
1 Definition
1.1 A single charged particle
1.2 Multiple charged particles
1.3 In terms of momentum
2 Analogy with a classical dipole
3 Origin
4 Applications
5 See also
6 References
Definition
A single charged particle
For a transition where a single charged particle changes state from {\displaystyle
|\psi _{a}\rangle } |\psi _{a}\rangle to {\displaystyle |\psi _{b}\rangle } |\psi
_{b}\rangle , the transition dipole moment {\displaystyle {\text{(t.d.m.)}}}
{\text{(t.d.m.)}} is

{\displaystyle ({\text{t.d.m. }}a\rightarrow b)=\langle \psi _{b}|(q\mathbf

{r} )|\psi _{a}\rangle =q\int \psi _{b}^{*}(\mathbf {r} )\,\mathbf {r} \,\psi _{a}
(\mathbf {r} )\,d^{3}\mathbf {r} } {\displaystyle ({\text{t.d.m. }}a\rightarrow
b)=\langle \psi _{b}|(q\mathbf {r} )|\psi _{a}\rangle =q\int \psi _{b}^{*}(\mathbf
{r} )\,\mathbf {r} \,\psi _{a}(\mathbf {r} )\,d^{3}\mathbf {r} }
where q is the particle's charge, r is its position, and the integral is over all
space ( {\displaystyle \int d^{3}\mathbf {r} } \int d^{3}{\mathbf {r}} is
shorthand for {\displaystyle \iiint dx\,dy\,dz} \iiint dx\,dy\,dz). The transition
dipole moment is a vector; for example its x-component is

{\displaystyle ({\text{x-component of t.d.m. }}a\rightarrow b)=\langle \psi _{b}|

(qx)|\psi _{a}\rangle =q\int \psi _{b}^{*}(\mathbf {r} )\,x\,\psi _{a}(\mathbf
{r} )\,d^{3}\mathbf {r} } {\displaystyle ({\text{x-component of
t.d.m. }}a\rightarrow b)=\langle \psi _{b}|(qx)|\psi _{a}\rangle =q\int \psi
_{b}^{*}(\mathbf {r} )\,x\,\psi _{a}(\mathbf {r} )\,d^{3}\mathbf {r} }
In other words, the transition dipole moment can be viewed as an off-diagonal
matrix element of the position operator, multiplied by the particle's charge.

Multiple charged particles

When the transition involves more than one charged particle, the transition dipole
moment is defined in an analogous way to an electric dipole moment: The sum of the
positions, weighted by charge. If the ith particle has charge qi and position
operator ri, then the transition dipole moment is:

{\displaystyle ({\text{t.d.m. }}a\rightarrow b)=\langle \psi _{b}|(q_{1}\mathbf {r}

_{1}+q_{2}\mathbf {r} _{2}+\cdots )|\psi _{a}\rangle =} {\displaystyle
({\text{t.d.m. }}a\rightarrow b)=\langle \psi _{b}|(q_{1}\mathbf {r}
_{1}+q_{2}\mathbf {r} _{2}+\cdots )|\psi _{a}\rangle =}
{\displaystyle =\int \psi _{b}^{*}(\mathbf {r} _{1},\mathbf {r} _{2},\ldots )\,
(q_{1}\mathbf {r} _{1}+q_{2}\mathbf {r} _{2}+\cdots )\,\psi _{a}(\mathbf {r}
_{1},\mathbf {r} _{2},\ldots )\,d^{3}\mathbf {r} _{1}\,d^{3}\mathbf {r}
_{2}\cdots } {\displaystyle =\int \psi _{b}^{*}(\mathbf {r} _{1},\mathbf {r}
_{2},\ldots )\,(q_{1}\mathbf {r} _{1}+q_{2}\mathbf {r} _{2}+\cdots )\,\psi _{a}
(\mathbf {r} _{1},\mathbf {r} _{2},\ldots )\,d^{3}\mathbf {r} _{1}\,d^{3}\mathbf
{r} _{2}\cdots }
In terms of momentum
For a single, nonrelativistic particle of mass m, in zero magnetic field, the
transition dipole moment can alternatively be written in terms of the momentum
operator, using the relationship[1]

{\displaystyle \langle \psi _{a}|\mathbf {r} |\psi _{b}\rangle ={\frac {i\hbar }

{(E_{b}-E_{a})m}}\langle \psi _{a}|\mathbf {p} |\psi _{b}\rangle } \langle \psi
_{a}|{\mathbf {r}}|\psi _{b}\rangle ={\frac {i\hbar }{(E_{b}-E_{a})m}}\langle
\psi _{a}|{\mathbf {p}}|\psi _{b}\rangle
This relationship can be proven starting from the commutation relation between
position x and the Hamiltonian H:

{\displaystyle [H,x]=\left[{\frac {p^{2}}{2m}}+V(x,y,z),x\right]=\left[{\frac

{p^{2}}{2m}},x\right]={\frac {1}{2m}}(p_{x}[p_{x},x]+[p_{x},x]p_{x})=-i\hbar
p_{x}/m} {\displaystyle [H,x]=\left[{\frac {p^{2}}{2m}}
+V(x,y,z),x\right]=\left[{\frac {p^{2}}{2m}},x\right]={\frac {1}{2m}}(p_{x}
[p_{x},x]+[p_{x},x]p_{x})=-i\hbar p_{x}/m}
Then

{\displaystyle \langle \psi _{a}|(Hx-xH)|\psi _{b}\rangle ={\frac {-i\hbar }

{m}}\langle \psi _{a}|p_{x}|\psi _{b}\rangle } \langle \psi _{a}|(Hx-xH)|\psi
_{b}\rangle ={\frac {-i\hbar }{m}}\langle \psi _{a}|p_{x}|\psi _{b}\rangle
However, assuming that ?a and ?b are energy eigenstates with energy Ea and Eb, we
can also write

{\displaystyle \langle \psi _{a}|(Hx-xH)|\psi _{b}\rangle =(\langle \psi _{a}|

H)x|\psi _{b}\rangle -\langle \psi _{a}|x(H|\psi _{b}\rangle )=(E_{a}-E_{b})\langle
\psi _{a}|x|\psi _{b}\rangle } \langle \psi _{a}|(Hx-xH)|\psi _{b}\rangle =(\langle
\psi _{a}|H)x|\psi _{b}\rangle -\langle \psi _{a}|x(H|\psi _{b}\rangle )=(E_{a}-
E_{b})\langle \psi _{a}|x|\psi _{b}\rangle
Similar relations hold for y and z, which together give the relationship above.

Analogy with a classical dipole

Main article: Electric dipole moment
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, {\displaystyle +q} {\displaystyle +q}
and {\displaystyle -q} -q, with a displacement vector, {\displaystyle \mathbf {r} }
\mathbf {r} , pointing from the negative charge to the positive charge, the
electric dipole moment is given by

{\displaystyle \mathbf {p} =q\mathbf {r} } {\mathbf {p}}=q{\mathbf {r}}.

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:

{\displaystyle |\mathbf {\tau } |=|q\mathbf {r} ||\mathbf {E} |\sin \theta } |

{\mathbf {\tau }}|=|q{\mathbf {r}}||{\mathbf {E}}|\sin \theta .
Similarly, the coupling between an electromagnetic wave and an atomic transition
with transition dipole moment {\displaystyle \mathbf {d} _{nm}} {\displaystyle
\mathbf {d} _{nm}} 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
{\displaystyle \omega } \omega , it can undergo a transition from an initial to a
final state of energy difference {\displaystyle \hbar \omega } \hbar \omega
through the coupling of the electromagnetic field to the transition dipole moment.
When this transition is from a lower energy state to a higher energy state, this
results in the absorption of a photon. A transition from a higher energy state to a
lower energy state results in the emission of a photon. If the charge,
{\displaystyle e} e, is omitted from the electric dipole operator during this
calculation, one obtains {\displaystyle \mathbf {R} _{\alpha }} {\displaystyle
\mathbf {R} _{\alpha }} 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
{\displaystyle \pi } \pi orbital to an antibonding {\displaystyle \pi ^{*}} \pi^*
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 {\displaystyle \mathbf {r} } \mathbf {r} , 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. The transition moment integral

{\displaystyle \int \psi _{1}^{*}\mu \psi _{2}d\tau } \int \psi _{1}^{*}\mu \psi
_{2}d\tau ,
of an electronic transition within similar atomic orbitals, such as s-s or p-p, is
forbidden due to the triple integral returning an ungerade (odd) product. Such
transitions only redistribute electrons within the same orbital and will return a
zero product. If the triple integral returns a gerade (even) product, the
transition is allowed.