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If a gas is illuminated with a laser of a frequency less than (but more than half of) the work function of the atoms in the gas, the atoms will be excited into Rydberg atoms.

Is there a finite chance that the Rydberg atoms themselves will be hit by a second photon and thus be ionised?

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It is also possible for the ionization to take place via a nonlinear optical two-photon absorption (two photons being absorbed simultaneously). These events are more improbable than the single photon absorption, but their probability scales with the intensity of the light source so high power laser irradiation is certainly capable of producing them.

Lewis Miller
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  • Two-photon absorption has even become a lively research and trcnology topic these days. Neural researchers use it to select and activate individual neurons, and if you search the web, you can find amazing micro-sculptures created by using two-photon transitions. – Terry Bollinger Dec 22 '15 at 02:20
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Yes, an excited state can absorb more energy. So multiple photons can excite an electron through multiple levels, over time (assuming the orbital doesn't lose its energy in the mean time). Of course, no single photon can excite more than its energy.

Digiproc
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