Atoms in electric fields
This section deals with how atoms behave in static electric fields. The method is straightforward, involving second order perturbation theory. The treatment describes the effects of symmetry on the basic interaction, polarizability, and the concept of oscillator strength.
Contents
- 1 Review: Parity
- 2 Review: Results of Stationary Perturbation Theory
- 3 Supplement: The Hydrogen Atom in a Static Electric Field
- 4 Perturbation Theory of Polarizability
- 5 Beyond the quadratic Stark effect
- 6 Field ionization
- 7 Atoms in an Oscillating Electric Field
- 8 Oscillator Strength
- 9 Index of refraction
- 10 References
Review: Parity
Review: Results of Stationary Perturbation Theory
Supplement: The Hydrogen Atom in a Static Electric Field
Perturbation Theory of Polarizability
We will find the energy and polarizability of an atom in a static field along the +z direction. We apply perturbation theory taking to describe the unperturbed atomic system and
Non-degenerate eigenstates have to be eigenstates of parity. Since is odd under parity operation, parity requires that . So the first order perturbation vanishes. To second order, the energy is given by
If we define now the polarizability in state as
- {EQ_polarsix}
we obtain
The dipole moment is the expectation value of the dipole operator, using the first order perturbed state vector.
where the sum is over Only the term will contribute, and we can express the induced dipole moment by the polarizability:
Note that the Stark shift is and not equal to . is the expectation value for the electrostatic potential energy of the dipole moment, but the total energy change is only one half of this since energy is needed to admix excited states into the ground state.
Note that polarizability has the dimensions of length, i.e. volume. As an example, for the ground state of hydrogen we can obtain a lower limit for the polarizability by considering only the contribution to the sum of the state. Values for the various moments in hydrogen are given in Bethe and Salpeter, Section 63. Using = 1.666, and , we obtain atomic units (i.e. ).
The polarizability of the ground state of hydrogen can be calculated exactly. It turns out that the state makes the major contribution, and that the higher bound states contribute relatively little. However, the continuum makes a significant contributions. The exact value is 4.5.
To put the above result for the polarizability in perspective, note that the potential of a conducting sphere of radius in a uniform electric field is given by
The induced dipole moment is , so that the polarizability is . For the ground state of hydrogen, , so to a crude approximation, in an electric field hydrogen behaves like a conducting sphere.
Polarizability may be approximated easily, though not accurately, using Unsold's approximation in which the energy term in the denominator of Eq. \ref{EQ_polarsix} is replaced by an average energy interval . The sum can then be evaluated using the closure rule . (Note that the term does not need to be excluded from the sum, since .). With this approximation,
For hydrogen in the ground state, . If we take the average excitation energy to be , the result is .
If we use the virial theorem for the ground state energy, and use we obtain
which shows that the polarizability is related to the atomic volume.
Beyond the quadratic Stark effect
It should be obvious from the previous discussion that the Stark effect for a state of is quadratic only when
(EQ_ beyondone)
when is the nearest state of opposite parity to .
If is the ground state, we can expect Hartree and (virial theorem). Hence the Stark shift should be quadratic if the field is well below the critical value
(EQ_ beyondtwo)
[ is atomic unit of field] —a field three orders of magnitude in excess of what can be produced in a laboratory except in a vanishingly small volume.
If is an excited state, say , this situation changes dramatically. In general, the matrix element and to the next level of opposite parity depends on the quantum defect:
(EQ_ beyondthree)
Thus the critical field is lowered to
(EQ_ beyondfour)
Considering that quantum defects are typically when is the largest of an electron in the core), it is clear that even 1 V/cm fields will exceed for higher levels if . Large laboratory fields ( V/cm) can exceed even for states if .
When the electric field exceeds states with different but the same are degenerate to the extent that their quantum defects are small. Once exceeds the number of core electrons, these states will easily become completely mixed by the field and they must be diagonalized exactly. The result is eigenstates possessing apparently permanent electric dipoles with a resulting linear Stark shift (see following figure). As the field increases, these states spread out in energy. First they run into states with the same but different quantum defects; then the groups of states with different begin to overlap. At this point a matrix containing all states with greater or equal to must be diagonalized. Only the lowest states do not partake in this strong mixing.
The situation described above differs qualitatively for hydrogen since it has no quantum defects and the energies are degenerate. In this case the zero-field problem may be solved using a basis which diagonalizes the Hamiltonian both for the atom above and also in the presence of an electric field. This approach corresponds to solving the H atom in parabolic–ellipsoidal coordinates and results in the presence of an integral quantum number which replaces . The resulting states possess permanent dipole moments which vary with this quantum number and therefore have linear Stark effects even in infinitesimal fields. Moreover the matrix elements which mix states from different manifolds vanish at all fields, so the upper energy levels from one manifold cross the lower energy levels from the manifold above without interacting with them.
The following example shows the high field Stark effect for Li. Only the term in Li has an appreciable quantum defect, and it has been suppressed by selecting final states with .
The dramatic difference between the physical properties of atoms with and the properties of the same atoms in their ground state, coupled with the fact that these properties are largely independent of the type of atom which is excited, justifies the application of the name Rydberg atoms to highly excited atoms in general. Rydberg atoms have been pioneered by the groups of Kleppner, Haroche, Walther.
\caption{ Stark effect and field ionization in Li for levels with . Each vertical line in (a)represents a measurement at that field of the number of atoms excited (from the state) by radiation whose energy falls the indicated amount below the ionization limit. Thus the patterns made by absorption peaks at successive field strengths represent the behavior of the energy levels with increasing field. At zero field the levels group according to the principal quantum number ; at intermediate field the levels display a roughly linear Stark effect, and at high fields they disappear owing to field ionization. The solid line is the classically predicted ionization field (see next section). Figure taken from M.G. Littman, M.M. Kash and D. Kleppner, Phys. Rev. Lett. 41, 103–107 (1978).}
Field ionization
If an atom is placed in a sufficiently high electric field it will be ionized, a process called field ionization . An excellent order of magnitude estimate of the field , required to ionize an atom which is initially in a level bound by energy can be obtained by the following purely classical argument: the presence of the field adds the term to the potential energy of the atom. This produces a potential with a maximum and the atom will ionize if Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U_{\rm max} < -E} .
The figure shows the combined potential as well as Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U_{\rm atom}} and Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U_{\rm field}} .
\caption{Potential diagram for field ionization. }
Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{align} \ U_{\rm total}(z) = U_{\rm atom} (z) + U_{\rm field}(z) = \frac{-e^2}{ | z |} + e\epsilon z \end{align}} (EQ_ fieldionone)
The appropriate maximum occurs at
Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{align} \ z_{\rm max} = - {\left(\frac{e}{\epsilon }\right)^{1/2}} \end{align}} (EQ_ fieldiontwo)
as determined from Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle dU/dz = 0} . Equating Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U_{\rm max}=-2 e^{3/2} \epsilon^{1/2}} and Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -E=-Ryd/n^2} gives
Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \begin{align} \ \epsilon _{ion} = \frac{E^2}{4e^2} = \frac{1}{16n^{*4}} \frac{e}{a_0^2}= 3.2\times 10^8 (n^*)^{-4} \ {\rm V/cm} \end{align}} (EQ_ fieldionthree)
for level with energy Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -E} and quantum number Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle n^*} .
The predictions of this formula for Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E_{\rm ion}} is usually accurate within 20% in spite of its neglect of both quantum tunneling and the change in Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E} produced by the field. Tunneling manifests itself as a finite decay rate for states which classically lie lower than the barrier. The increase of the ionization rate with field is so dramatic, however, that the details of the experiment do not influence the field at which ionization occurs very much: calculations [u'BHR65'] show the ionization rate increasing from Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 10^5} /sec to Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle 10^{10}} /sec for a 30% increase in the field.
Oddly enough the classical prediction works worse for H than for any other atom. This is a reflection of the fact that certain matrix elements necessary to mix the Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle n,\ell } states (so the wave function samples the region near Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle U_{\rm max}} ) are rigorously zero in H, as discussed in the preceding part of this section. Hence the orbital ellipse of the electron does not precess and can remain on the side of the nucleus. There its energy will increase with Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \epsilon } , but it will not spill over the lip of the potential and ionize.
Field ionization is an important technique with applications in applied and fundamental science. Its important feature is close to 100 % detection efficiency for atoms excited to Rydberg states.
Applied application: Detection of trace elements. After Chernobyl, field ionization techniques were refined to detect radioactive strontium isotopes or other radio-isotopes. The spectroscopic scheme was excitation to Rydberg states (which is isotope specific thanks to isotope shifts), followed by field ionization. See, e.g. Wendt et al., Physica Scripta T58, 104-108 (1995).
Fundamental physics: Field ionization has been used by Haroche's and Walther's group for a series of studies of Rydberg atoms exchanging photons with a microwave cavity, e.g. for the single atom maser experiment, or for other QED studies. See, e.g. Brune et al., Phys. Rev. Lett. 76, 1800 (1996).
Atoms in an Oscillating Electric Field
There is a close connection between the behavior of an atom in a static electric field and its response to an oscillating field, i.e. a connection between the Stark effect and radiation processes. In the former case, the field induces a static dipole moment; in the latter case, it induces an oscillating moment. An oscillating moment creates an oscillating macroscopic polarization and leads to the absorption and emission of radiation. We shall calculate the response of an atom to an oscillating field
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathcal{E} (\omega , t) \hat{e} = \mathcal{E} \hat{e} \cos\omega t }
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hat{e}} is the polarization vector for the field. For a weak field the time varying state of this system can be found from first order time dependent perturbation theory. We shall write the electric dipole operator as D = -er. (This is a change of notation. Previously the symbol was d.) The Hamiltonian naturally separates into two parts, Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H= H_0 + H^\prime (t)} , where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H_0} is the unperturbed Hamiltonian and
{EQ_atomoef2}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H^\prime = -D \cdot \hat{e} \mathcal{E} \cos \omega t = - \frac{1}{2} (e^{i\omega t} + e^{-i\omega t} ) \mathcal{E} \hat{e} \cdot D }
We shall express the solution of the time dependent Schroedinger equation in terms of the eigenstates of Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H_0 , |n \rangle } .
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle | \psi \rangle = \sum_{n} a_n e^{-i\omega_n t} | n \rangle ~~~H_0 |\psi \rangle = \hbar \sum_{n} a_n \omega_n e^{-i\omega_n t} |n \rangle }
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_n = E_n/\hbar} . Because of the perturbation Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H^\prime (t)} , the Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_n} 's become time dependent, and we have
Left multiplying the final two expressions by Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle k|} to project out the Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle k} -th terms yields
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \dot{a}_k = (i\hbar )^{-1} \sum_{n} \langle k | H^\prime (t) |n \rangle a_n e^{i\omega_{kn} t} }
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_{kn} = \omega_k - \omega_n} . In perturbation theory, this set of equations is solved by a set of approximations to Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_k} labeled Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_k^{(i)} (t)} . Starting with
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_n^{(0)} (t) = a_n (0) }
one sets
{EQ_atomoef7}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \dot{a}_k^{(i+1)} (t) = (i\hbar )^{-1} \sum_{n} \langle k |H^\prime (t) |n \rangle a_n^{(i)} (t) e^{i\omega_{kn} t} }
and solves for the successive approximations by integration.
We now apply this to the problem of an atom which is in its ground state Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle g} at Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t=0} , and which is subject to the interaction of Eq. \ref{EQ_atomoef2}. Consequently Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_g (0) = 1} , Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle a_{n\not= g} (0) = 0} . Substituting in Eq. \ref{EQ_atomoef7} and integrating from Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t^\prime = 0} to Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t} gives
The -1 terms in the square bracketed term arises because it is assumed that the field was turned on instantaneously at Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle t=0} . They represent transients that rapidly damp and can be neglected.
The term with Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_{kg} + \omega} , in the denominator is the counter-rotating term. It can be neglected if one is considering cases where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega \approx \omega_{kg}} (i.e. near resonance), but we shall retain both terms and calculate the expectation value of the first order time dependent dipole operator Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle D (\omega ,t) \rangle }
If we consider the case of linearly polarized light Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle (\hat{e} = \hat{z})} , then
{EQ_atomoef10}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle d_z (\omega , t) = \frac{2e^2}{\hbar} \sum_{k} \frac{\omega_{kg} | \langle k|z|g \rangle |^2}{\omega_{kg}^2 - \omega^2} \mathcal{E} \cos \omega t }
We can write in terms of a polarizability Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \alpha (\omega )} :
{EQ_atomoef11}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \alpha (\omega ) = \frac{2e^2}{\hbar} \sum_{k} \frac{\omega_{kg} | \langle k|z|g \rangle |^2}{\omega_{kg}^2 - \omega^2} }
This result diverges if Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega \rightarrow \omega_{kg}} . Later, when we introduce radiative damping, the divergence will be avoided in the usual way. The AC Stark shift is given by Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -\frac{1}{2}\alpha(\omega) \overline{\mathcal{E}(t)^2} } where the bar denotes the time average over the rapidly oscillating electric field.
For Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega \rightarrow 0} one retrieves the result for the DC Stark effect. Note that in the DC limit, the co- and counter-rotation terms contribute equally.
The AC Stark shift Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Delta E} can be expressed by the Rabi frequency Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \hbar \omega_R= -e \mathcal{E} \langle e|z|g \rangle } as
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Delta E=-\frac{\hbar}{4} \omega_R^2 \left(\frac{1}{-\delta}+\frac{1}{2\omega-\delta} \right) }
This looks very similar to the result of time-independent perturbation theory, where the energy shift is the matrix element squared over the detuning. Here, we have the matrix element and two terms with detunings Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \delta} and Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -(2\omega-\delta)} , respectively. This result emerges very naturally in the dressed atom picture which will be discussed later. Here, one considers the combined states of the atoms and the photon field. The ground state with N photons, Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle |g \rangle + N \gamma } interacts with the states at detuning Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \delta} and the state Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle |e\rangle + (N+1) \gamma } at detuning Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -(2\omega-\delta)} .
Oscillator Strength
Eq. \ref{EQ_atomoef11} resemble the oscillating dipole moment of a system of classical oscillators. Consider a set of oscillators having charge Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle q_k} , mass Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle m} , and natural frequency Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_k} , driven by the field Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \mathcal{E} \cos \omega t} . The amplitude of the motion is given by
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle z_k = \frac{q_k}{m(\omega_k^2 - \omega^2)} \mathcal{E} \cos \omega t }
If we have a set of such oscillators, then the total oscillating moment is given by
{EQ_ostre2}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle d_z (\omega , t) = \frac{1}{m} \sum_{k} \frac{q_k^2}{(\omega_k^2 - \omega^2)} \mathcal{E} \cos \omega t }
This is strongly reminiscent of Eq. \ref{EQ_atomoef10}. It is useful to introduce the concept of oscillator strength, a dimensionless quantity defined as
{EQ_ostre3}
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle k} and Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle j} are any two eigenstates. Note that Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f_{kj}} is positive if Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle E_k > E_j} , i.e. for absoprtion, and negative if Then, Eq. \ref{EQ_atomoef10} becomes
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle d_z (t) = \sum_{k} f_{kg} \frac{e^2}{m(\omega_{kg}^2 - \omega^2 )} \mathcal{E} \cos \omega t }
Comparing this with Eq. \ref{EQ_ostre2}, we see that the behavior of an atom in an oscillating field mimics a set of classical oscillators with the same frequencies as the eigenfrequencies of the atom, but having effective charge strengths Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle q_k^2 = f_{kg} e^2} .
The oscillator strength is useful for characterizing radiative interactions and also the susceptibiltiy of atoms for three reasons:
(1) It emphasizes the classical correspondence
(2) It satisfies a sum rule
(3) It provides a dimensionless parameter characterizing the coupling of the atom to the external field
The oscillator strength satisfies the Thomas-Reiche-Kuhn sum rule:
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sum_{k} f_{kg} = 1 }
The proof is often presented in quantum mechanics classes. Since it is short, we repeat it here.
We prove by considering the general Hamiltonian
{EQ_ostre6}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle H= \frac{1}{2} \sum_{j} p_j^2 + V(r_1 , r_2 \cdots ) . }
Using the commutator relation
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle [A,B^2] = [A,B] B+ B [A,B], }
and the relation Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle [r_j , p_k] = i\hbar\delta_{jk}} , we have
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle [r,H] = \frac{i\hbar}{m} p }
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle r = \sum r_j} , and Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle p = \sum p_j} . However,
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle j | [r, H] |k \rangle = (E_k - E_n ) \langle j | r | k \rangle }
Consequently,
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \langle j | r |k \rangle = \frac{i}{m} \frac{ \langle j|p |k \rangle }{\omega_{kj} } }
where Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_{kj} = (E_k - E_j )/\hbar} . Thus, we can write Eq. \ref{EQ_ostre3} in either of two forms:
Taking half the sum of these equations and using the closure relation Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sum_{k} |k \rangle \langle k|=1} , we have
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sum_{k} f_{kj} = \frac{i}{\hbar} {\left[ \langle j |p_z z - z p_z | j \rangle \right]} = 1 }
We have calculated this for a one-electron atom, but the application to a Z-electron atom is straightforward because the Hamiltonian in Eq. \ref{EQ_ostre6} is quite general. In this case
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sum_{k} f_{kj} = Z . }
Here is some eigenstate of the system, and the index Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle k} describes all the eigenstates of all the electrons -- including continuum states. In cases where only a single electron will be excited, however, for instance in the optical regime of a "single-electron" atom where the inner core electrons are essentially unaffected by the radiation, the atom behaves as if it were a single electron system with Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle Z=1} .
Note that Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f_{kj}} is positive if Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \omega_{kj} > 0} , i.e. if the final state lies above the initial state. Such a transition corresponds to absorption of a photon. Since Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f_{jk} = -f_{jk}} , the oscillator strength for emission of a photon is negative.
For hydrogen, the 1s 2p transition has an oscillator strength of 0.4162. Often, assuming Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle f \approx 1} for the strongest transition gives a good order of magnitude approximation.
For the alkalis, the D line has an oscillator strength of close to 1. Therefore, knowledge of the resonance frequency is sufficient to calculate Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \alpha} and also the natural linewidth .
The matrix element can be expressed by the oscillator strength using Eq. \ref{EQ_ostre3}:
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle = \frac{2m}{\hbar} \omega_{kj} | \langle k|z|j \rangle |^2 = f_{kj} \frac{1}{2} \bar{\lambda}_{compton}\bar{\lambda} }
which implies that for a strong transition, the matrix element is the geometric mean of Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \bar{\lambda}_{compton}} and .
Index of refraction
As an application of the expression for the ac polarizability, we now discuss the index of refraction of an atomic gas. What we derive here, is fully sufficient to understand both absorption imaging and phase-contrast imaging used to observe ultracold atomic clouds.
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle n_r = \sqrt{1 + 4 \pi n_{at} \alpha} \approx 1 + 2 \pi n_{at} \alpha }
In the case of near resonant light we can neglect the counter-rotating term, and let
Define the natural linewidth (this expression is derived later in the course)
So we can rewrite the expression for the refractive index:
where, since
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \frac{c^3}{\omega^3}=\frac{\lambda^3}{(2\pi)^3} }
we have
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sigma_0 \equiv 6\pi\bigg(\frac{\lambda}{2\pi}\bigg)^2 }
In our derivation of the polarizability, we didn't include any damping. The effect of damping is to give the refractive index an imaginary (absorptive) part. Damping can be included by adding an imaginary part to the detuning Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \delta} :
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \delta \rightarrow \delta + i \frac{\gamma}{2} }
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle -\frac{\Gamma}{2\delta}\rightarrow \frac{\Gamma}{\gamma}\bigg(\frac{-1}{\delta'+i}\bigg)=\frac{\Gamma}{\gamma}\bigg[\frac{i}{1+\delta'^2}-\frac{\delta'}{1+\delta'^2}\bigg] }
where the first term in brackets corresponds to dispersion and the second to absorption. This become obvious when one propagates the wave with the wavevector modified by the index of refraction:
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle e^{ikz}=e^{in_{r}\frac{\omega}{c}z}=e^{-\frac{D_0}{2}[\frac{1}{1+\delta'^2}-\frac{i\delta'}{1+\delta'^2}]} }
The optical density on resonance is:
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle D_0 = n_{at}\sigma_0 \frac{\Gamma}{\gamma}z }
Note: When the linewidth is determined by spontaneous emission then Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \gamma = \Gamma} , and the dispersive phase shift is
The maximum phase shift occurs at a detuning of Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \delta' = \pm 1}
- Failed to parse (MathML with SVG or PNG fallback (recommended for modern browsers and accessibility tools): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \phi = \mp \frac{D_0}{4} }