Photofragment-ion Imaging - The Product Imaging Technique

The Product Imaging Technique

In the original product imaging paper, the positions of the ions are imaged onto a two-dimensional detector. A photolysis laser dissociates methyl iodide (CH₃I), while an ionization laser is used REMPI to ionize a particular vibrational level of the CH₃ product. Both lasers are pulsed, and the ionization laser is fired at a delay short enough that the products have not moved appreciably. Because ejection of an electron by the ionization laser does not change the recoil velocity of the CH₃ fragment, its position at any time following the photolysis is nearly the same as it would have been as a neutral. The advantage of converting it to an ion is that, by repelling it with a set of grids (represented by the vertical solid lines in the figure), one can project it onto a two-dimensional detector. The detector is a double microchannel plate consisting of two glass discs with closely packed open channels (several micrometres in diameter). A high voltage is placed across the plates. As an ion hits inside a channel, it ejects secondary electrons that are then accelerated into the walls of the channel. Since multiple electrons are ejected for each one that hits the wall, the channels act as individual particle multipliers. At the far end of the plates approximately 107 electrons leave the channel for each ion that entered. Importantly, they exit from a spot right behind where the ion entered. The electrons are then accelerated to a phosphor screen, and the spots of light are recorded with a gated charge-coupled device (CCD) camera. The image collected from each pulse of the lasers is then sent to a computer, and the results of many thousands of laser pulses are accumulated to provide an image such as the one for ozone shown previously.

In this position-sensing version of product imaging, the position of the ions as they hit the detector is recorded. One can imagine the ions produced by the dissociation and ionization lasers as expanding outward from the center-of-mass with a particular distribution of velocities. It is this three-dimensional object that we wish to detect. Since the ions created should be of the same mass, they will all be accelerated uniformly toward the detector. It takes very little time for the whole three-dimensional object to be crushed into the detector, so the position of an ion on the detector relative to the center position is given simply by v Δt, where v is its velocity and Δt is the time between when the ions were made and when they hit the detector. The image is thus a two-dimensional projection of the desired three-dimensional velocity distribution. Fortunately, for systems with an axis of cylindrical symmetry parallel to the surface of the detector, the three-dimensional distribution may be recovered from the two-dimensional projection by the use of the inverse Abel transform. The cylindrical axis is the axis containing the polarization direction of the dissociating light. It is important to note that the image is taken in the center-of-mass frame; no transformation, other than from time to speed, is needed.

A final advantage of the technique should also be mentioned: ions of different masses arrive at the detector at different times. This differential arises because each ion is accelerated to the same total energy, E, as it traverses the electric field, but the acceleration speed, v_z, varies as E = ½ mv_z2. Thus, v_z varies as the reciprocal of the square root of the ion mass, or the arrival time is proportional to the square root of the ion mass. In a perfect experiment, the ionization laser would ionize only the products of the dissociation, and those only in a particular internal energy state. But the ionization laser, and perhaps the photolysis laser, can create ions from other material, such as pump oil or other impurities. The ability to selectively detect a single mass by gating the detector electronically is thus an important advantage in reducing noise.