Arrival time

Digital Signal Processor board fPSP) it is hosted into the PC and processes in real time the binary sequences stored into the acquisition board FIFO memories. The board processes arrival times and extracts the correlated AT generated by AE events. The PC picks up the data stored into the DSP memories and calculates the position of the AE sources. 

A number of individual radar scans have been joined together Variations in cover depth give rise to variations in arrival time for the wave reflected from the reinforcing bars... 

Finally, tlie ability to optically address single molecules is enabling some beautiful experiments in quantum optics. The non-Poissonian photon arrival time distributions expected tlieoretically for single molecules have been observed directly, botli antibunching at short times [112] and bunching on longer time scales [6, 112 and 113]. The fluorescence excitation spectra of single molecules bound to spherical microcavities have been examined as a probe... 

For either the in-line or hybrid analyzers, the ions injected into the TOF section must all begin their flight down the TOF tube at the same instant if arrival times of ions at a detector are to be used to measure m/z values (see Chapter 26, TOF Ion Optics ). For the hybrid TOF instruments, the ion detector is usually a microchannel plate ion counter (see Chapter 30, Comparison of Multipoint Collectors (Detectors) of Ions Arrays and MicroChannel Plates ). 

As m increases, At becomes progressively smaller (compare the difference between the square roots of 1 and 2 (= 0.4) with the difference between 100 and 101 (= 0.05). Thus, the difference in arrival times of ions arriving at the detector become increasingly smaller and more difficult to differentiate as mass increases. This inherent problem is a severe restriction even without the second difficulty, which is that not all ions of any one given m/z value reach the same velocity after acceleration nor are they all formed at exactly the same point in the ion source. Therefore, even for any one m/z value, ions at each m/z reach the detector over an interval of time instead of all at one time. Clearly, where separation of flight times is very short, as with TOF instruments, the spread for individual ion m/z values means there will be overlap in arrival times between ions of closely similar m/z values. This effect (Figure 26.2) decreases available (theoretical) resolution, but it can be ameliorated by modifying the instrument to include a reflectron. 

TOF mass spectrometers are very robust and usable with a wide variety of ion sources and inlet systems. Having only simple electrostatic and no magnetic fields, their construction, maintenance, and calibration are usually straightforward. There is no upper theoretical mass limitation all ions can be made to proceed from source to detector. In practice, there is a mass limitation in that it becomes increasingly difficult to discriminate between times of arrival at the detector as the m/z value becomes large. This effect, coupled with the spread in arrival times for any one m/z value, means that discrimination between unit masses becomes difficult at about m/z 3000. At m/z 50,000, overlap of 50 mass units is more typical i.e., mass accuracy is no better than about 50-100 mass... 

Since the microchannel plate collector records the arrival times of all ions, the resolution depends on the resolution of the TOP instrument and on the response time of the microchannel plate. A microchannel plate with a pore size of 10 pm or less has a very fast response time of less than 2 nsec. The TOP instrument with microchannel plate detector is capable of unit mass resolution beyond m/z 3000. 

Any one bin can be electronically distinguished from the next one, and therefore the bins can be used like the tick of a standard clock. Each bin serves as one tick, which lasts for only 0.3 nsec. By counting the ticks and knowing into which bin the ion pulse has gone, the time taken for the ion to arrive at the detector can be measured to an accuracy of 0.3 nsec, which is the basis for measuring very short ion arrival times after the ions have traveled along the TOE analyzer tube. Each ion arrival pulse (event) is extracted from its time bin and stored in an associated computer memory location. 

Each bin is connected to a memory location in a computer so that each event can be stored additively over a period of time. All the totaled events are used to produce a histogram, which records ion event times versus the number of times any one event occurs (Figure 31.5).With a sufficiently large number of events, these histograms can be rounded to give peaks, representing ion m/z values (from the arrival times) and ion abundances (from the number of events). As noted above, for TOP instruments, ion arrival times translate into m/z values, and, therefore, the time and abundance chart becomes mathematically an m/z and abundance chart viz., a normal mass spectrum is produced. 

A mass spectrum is a chart of ion abundances versus m/z values. It is shown above that the TDC measures ion arrival times, which are converted directly into m/z values. Notionally, the number of ions arriving at the detector at any one m/z value is equal to the number of events recorded (one... 

By use of an electrostatic ion mirror called a reflectron, arrival times of ions of the same m/z value at the detector can be made more nearly equal. The reflectron improves resolution of m/z values. 

The mass spectrum gives the abundances of ions for different times of arrival at the detector. Since the times are proportional to the square root of the m/z values, it is simple to convert the arrival times into m/z values. 

This timing is done electronically by using a microchannel array ion collector and time bins. The microchannel array sends an electrical pulse to a time bin. Since a pulse is recorded, the ion arrival times are already digitized, hence the name time-to-digital converter (TDC). 

Ion arrival times are not adjusted, and the observed m/z values are just those originally measured. 

This reduction in information is achieved by a preprocessor, which uses the digital voltages corresponding to an ion peak to estimate the peak area (ion abundance) and centroid (mean arrival time of peak, equivalent to m/z value) these two pieces of information — plus a flag to identify the peak — are stored. 

Arrival time gauges alone can lead to equation-of-state data in other ways, as well, but they are most often used in conjunction with other gauges to be described later. Three different arrival time gauges are discussed below. 

Shock Luminescence. Some transparent materials give off copious amounts of light when shocked to a high pressure, and thus they can serve as shock arrival-time indicators. A technique used by McQueen and Fritz (1982) to measure arrival times of release waves is based on the reduction of shock-induced luminescence as the shock pressure is relieved. Bromoform, fused quartz, and a high-density glass have been used for their shock luminescence properties. 

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