Rydberg states pulsed-field ionization

T. P. Softley The aims of ZEKE spectroscopy are conceptually different from the atomic pulsed-field ionization experiments that predate ZEKE. In the latter, the aim is always to observe and study the individual Rydberg states. In ZEKE spectroscopy the aim is to detect small batches of Rydberg states lying below successive vibration-rotation thresholds of the ion without specific interest in the individual Ryd-... 

B. Kohler My question to T. Softley ties in to one of the major themes of the meeting, namely coherence. In your presentation you briefly mentioned that it may be important to consider an initially coherent superposition of states in the preparation step of experiments on highly excited Rydberg states. Several groups have now prepared coherent electronic wavepackets using picosecond (and shorter) pulses. Would this kind of an initial state be useful for any of the classes of pulsed-field ionization experiments that you have described ... 

A somewhat more advantageous ZEKE electron detection mechanism consists of pulsed-field ionization (PFI) of Rydberg states. In this schema, the photons do not populate the ion state directly, but rather very high Rydberg states that are convergent on... 

The ZEKE detection scheme is equivalent to ionization of high-n Rydberg states by Pulsed Field Ionization (PFI). If one assumes that the pulsed field ionization of the Rydberg electron follows a diabatic process (Chupka, 1993), then the ionization threshold is lowered by... 

Deviations from predicted rotational intensity distributions are very common in ZEKE spectra. This is due to random near coincidence between extremely numerous rapidly- and slowly-autoionizing resonances (Rydberg series converging to excited rovibronic states of the ion). Since the waiting time between excitation and pulsed field ionization is long, and the very weak DC and stray electric fields present during the ZEKE waiting period can induce weak interactions... 

An extension of ZEKE spectroscopy is mass-analysed threshold ionization (MATI), photoelectron spectroscopy without photoelectrons . This is effectively the same experiment for every ZEKE electron produced, there must be a cation, and in MATI detection a signal is recorded from these ions. It is much harder to separate the ions produced from pulsed-field ionization of the ZEKE Rydberg states from the ever-present directly produced ions. Ions are much heavier than electrons and hence move more slowly, so a higher-voltage extraction pulse is required for the separation and the subsequent extraction and selection of the cations. The obvious advantage of this combination of ZEKE with mass spectrometry is the ability to select the cations on the basis of their mass. 

Because it can be efficient and selective, field ionization of Rydberg atoms has become a widely used tool.1 Often the field is applied as a pulse, with rise times of nanoseconds to microseconds,2"4 and to realize the potential of field ionization we need to understand what happens to the atoms as the pulsed field rises from zero to the ionizing field. In the previous chapter we discussed the ionization rates of Stark states in static fields. In this chapter we consider how atoms evolve from zero field states to the high field Stark states during the pulse. Since the evolution depends on the risetime of the pulse, it is impossible to describe all possible outcomes. Instead, we describe a few practically important limiting cases. 

The second approach is to use thermal beams of alkali atoms as shown in Fig. 10.2.4 A beam of alkali atoms passes into a microwave cavity where the atoms are excited by pulsed dye lasers to a Rydberg state. A1 /zs pulse of microwave power is then injected into the cavity. After the microwave pulse a high voltage pulse is applied to the septum, or plate, inside the cavity to analyze the final states after interaction with the microwaves. By adjusting the voltage pulse it is possible to detect separately atoms which have and have not been ionized or to analyze by selective field ionization the final states of atoms which have made transitions to other bound states. 

While ionization by linearly polarized fields has been well studied, there is only one report of ionization by a circularly polarized field, the ionization of Na by an 8.5 GHz field.36 In the experiment Na atoms in an atomic beam pass through a Fabry-Perot microwave cavity, where they are excited to a Rydberg state using two pulsed tunable dye lasers tuned to the 3s — 3p and 3p —> Rydberg transitions at 5890 A and —4140 A respectively. The atoms are excited to the Rydberg states in the presence of the circularly polarized microwave field which is turned off 1 fis after the laser pulses. Immediately afterwards a pulsed field is applied to the atoms to drive any ions produced by microwave ionization to a microchannel plate detector. To measure the ionization threshold field the ion current is measured as the microwave power is varied. 

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