A two-photon transition transfers population through two interactions with the electric-dipole operator. For absorption of two photons,
The intermediate atomic states enter a second-order amplitude rather than necessarily being populated. Suppressing field-normalization factors, its structure is
Both time orderings contribute coherently. Close to a real intermediate resonance, linewidths and intermediate-state population must be treated explicitly; an off-resonant virtual-state approximation then ceases to be adequate. Well away from saturation the absorption rate scales as , or as for a single applied frequency.
Each electric-dipole interaction reverses parity, so two such interactions connect states of the same parity. The product operator contains angular tensor ranks , subject to triangle and polarization selection rules. Under the degenerate two-photon selection rule, identical equal-frequency photons have no antisymmetric rank-one contribution cancels; ranks zero and two remain. This permits a transition and excludes in that degenerate E1-E1 case. It does not universally forbid every transition, because a rank-two tensor can also connect some such pairs. For a single orbital electron, the corresponding orbital changes are , with spin unchanged in the nonrelativistic electric-dipole approximation.
In Doppler-free two-photon absorption, counterpropagating equal-frequency photons give first-order Doppler cancellation when one photon is absorbed from each beam:
The laser frequency is half the transition frequency. Same-beam two-photon events can still produce a broader Doppler-shifted background; residual beam-angle errors, unequal frequencies, AC Stark shifts and finite transit time limit precision. Thus a narrow two-photon resonance requires control of beam geometry and intensity, not just high laser power.
A stimulated Raman transition is the absorption-emission version: the atom absorbs from one beam and emits into the other, transferring between two long-lived states through an off-resonant upper state. It instead obeys
Counterpropagation now enhances momentum transfer rather than cancelling it. With single-photon Hamiltonian matrix elements and a common large angular detuning , eliminating the excited state gives
The two-photon detuning must include differential AC Stark and recoil shifts. Large detuning suppresses spontaneous scattering but also reduces coherent coupling at fixed optical power.
Figure 1.
two-photon absorption and stimulated Raman transfer have different energy and momentum sums
. Original level and photon-path schematics. A virtual intermediate line is not an additional stationary eigenstate; intermediate detunings are schematic, with no assumed atomic species or numerical level spacing. Details.
The coherent Raman route is useful for atomic beam splitters and mirrors. Mark Kasevich and Steven Chu demonstrated a laser-cooled sodium matter-wave interferometer using stimulated Raman transitions; its controlled internal-state changes accompanied separated external wave packets.[ref] Testing this interpretation requires scanning the two-photon detuning, controlling relative laser phase and checking output populations against pulse timing. A two-photon process is defined by its coherent two-interaction pathway; absorption-absorption and absorption-emission have different resonance and recoil conditions.