Detection, multiphoton events

Fig. 7.62 Detection of multiphoton events at low detector gain. Left Correctly recorded signal, recorded at a detector gain of 10° and a count rate of 3-7 10" s. Centre and right. The same signal recorded at a detector gain of 10 and 10". The light intensity was increased until the PMT signal triggered the CFD.

Luntz and co-workers have recently carried out an impressive study that follows in the spirit of the Eley-Rideal work.44 Specifically, laser-assisted recombination of N-atoms desorbing to form gas-phase N2 on Ru(0001) was investigated. Experimental measurements of state-selectively detected N2 recoiling from the surface recombination event were obtained using resonance enhanced multiphoton ionization and ion time-of-flight methods. In this way translational energy distributions of individual rovibrational states could be obtained experimentally. In addition, N2-vibrational population distributions could be derived. 

A more sophisticated mode of LIE detection is the multiphoton-excitation (MPE) fluorescence [47], which is based on the simultaneous absorption of more than one photon in the same quantum event and uses special lasers, such as femtosecond mode-locked laser [48] or continuous wave laser [49], This mode of LIE detection allows mass detection limits at zeptomole level (1 zepto-mole=10 mol) due to exceptionally low detection background and extremely small detection volume, whereas detection sensitivity in concentration is comparable to that of traditional LIE detection modes. A further drawback is the poor suitability of MPE-fluorescence detection to the on-column detection configuration, which is frequently employed in conventional LIE detection. 

A major advance in the utility of laser spectroscopy came as a result of the development of multiphoton ionization MPI as a means of detection of multiphoton absorption by molecules [1]. The resonance encountered as the n-photon energy of a scanning laser becomes coincident with that of a molecular excited state is evidenced by a large increase in ionization rate. Since single ionization events can be detected with near unit efficiency, this results in a very sensitive means of detecting weak multiphoton absorption. MPI is a more widely applicable method than laser induced fluorescence since it can be used for non-emitting states. 

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