1) Rydberg atoms are highly-excited atoms with loosely bound outer electrons that behave classically and are sensitive to microwave radiation.
2) The ionization of Rydberg atoms by microwaves shows a phenomenon called dynamical localization, where ionization is suppressed at certain frequencies due to quantum interference effects.
3) Calculations show that while hydrogen Rydberg atoms can be well described classically, alkali atoms exhibit different ionization behavior due to electron correlations within the atom core.
5. Bohr model of the hydrogen atom n = 3, E = -1.5 eV n = 12 E = -0.09 eV E = -9 kJ/mol E = -2 kcal/mol E = -800 cm -1 E = -20 THz n = 1 E = -13.6 eV 10 a.u. = 5.3 Å Rydberg electrons are weakly bound core electrons are tightly bound Microwave ionization involves ~ 200 photons at 10 GHz distances are to scale
6. Rydberg electrons are very sensitive to core electrons Accurate polarizabilities from Stark Effect H. Gould, T. M. Miller, Adv. At. Mol. Opt. Phys. 51 (2005), 343-361 E. L. Snow et. al. , Phys. Rev. A 71 (2005), art. no. 022510 Molecular fingerprinting J. L. Gosselin, P. M. Weber, J. Phys. Chem. A 109 (2005), 4899-4904 Electron energy/eV Intensity/a.u. Theory review: W. Clark, C. H. Greene, Rev. Mod. Phys. 71 (1999), 821-833 Electric field Energy same n, different l
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8. hydrogen atom a simple classical model explains its behavior well
9. The Bayfield-Koch experiment prepare Rydberg state take atoms out of storage microwave the atoms remove electrons Detect and record Hydrogen: J. E. Bayfield, P. M. Koch, Phys. Rev. Lett. 33 (1974), 258-261. Sodium: T. W. Ducas et. al. , Phys. Rev. Lett. 35 (1975), 366-369. Rubidium: L. Sirko, M. Arndt, P. M. Koch, H. Walther, Phys. Rev. A 49 (1994), 3831-3841. Lithium: C. H. Cheng, C .Y. Lee, T. F. Gallagher, Phys. Rev. A 54 (1996), 3303-3309. T. F. Gallagher, Rydberg Atoms , Cambridge Univ. Press, 2005 . Prevents ions from recombining with electrons H: electric discharge Alkali atoms: laser ablation Interaction time ~ 10 ns microwave resonator atomic beam excitation laser, e.g. CO 2 AC oscillator ion detector, e.g. mass spectrometer anode DC bias laser resonator
10. Field ionization mechanism R* + n ! R + + e - Combined potential Potential due to applied electric field Coulomb binding potential Classical energy of Rydberg electron position Energy
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14. Classical model predicts onset of anomaly P. M. Koch, Physica D 83 (1995), 178-205. Classical theory: Initial state is already chaotic Wrong scaling behavior Experiment and classical model agree well at low frequencies: Transition from regular to chaotic Negligible effect from tunneling There exists a frequency at which Rydberg H atoms ionize most easily! Experiment shows suppressed ionization threshold due to dynamical localization
Aluminum foil on a CD-ROM ionizing in a domestic microwave oven. Intro: Rydberg atoms are close to ionization threshold Correspondence principle => good for semiclassical theory Ionization behavior in microwave fields => good model for quantum chaos No well-defined adiabatic – nonadiabatic transition Anomalous diffusion rate in quantum chaos => dynamical localization Classical chaotic trajectories killed by interference with everything else The larger the path in phase space, the more likely it will die Compare with experiment. To do: Look up chemical applications of Anderson localization. Peter Wolynes.