Laser phase additivity

The role of the laser phase in controlling molecular dynamics was clear in the examples shown in Chapter 3, For example, in the one- vs. three-photon scenario the relative laser phase ( / 3 — 3c/ ,) enters directly into the interference term [see, e.g., Eq. (3.53)], as does the relative phase ((frl — (j 2) in the bichromatic control scenario [Eq. (3.19)]. These residts embody two useful general rules about the contribution of the laser phase to coherent control scenarios. The first is that the interference term contains the difference between the laser phase imparted to the molecule by one route, and that imparted to the molecule by an alternate route. Second, the phase imparted to the state Em) by a light field of the form  

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In addition to the loss of the 62 phase dependence, when the laser-phase matrix is time independent, the dependence on the phases of the other lasers is also lost as well. This is because the time-independent exp[— (0O 1 + + 1)] term factors out... 

Luminescence lifetime spectroscopy. In addition to the nanosecond lifetime measurements that are now rather routine, lifetime measurements on a femtosecond time scale are being attained with the intensity correlation method (124), which is an indirect technique for investigating the dynamics of excited states in the time frame of the laser pulse itself. The sample is excited with two laser pulse trains of equal amplitude and frequencies nl and n2 and the time-integrated luminescence at the difference frequency (nl - n2 ) is measured as a function of the relative pulse delay. Hochstrasser (125) has measured inertial motions of rotating molecules in condensed phases on time scales shorter than the collision time, allowing insight into relaxation processes following molecular collisions. 

For non-volatile sample molecules, other ionisation methods must be used, namely desorption/ionisation (DI) and nebulisation ionisation methods. In DI, the unifying aspect is the rapid addition of energy into a condensed-phase sample, with subsequent generation and release of ions into the mass analyser. In El and Cl, the processes of volatilisation and ionisation are distinct and separable in DI, they are intimately associated. In nebulisation ionisation, such as ESP or TSP, an aerosol spray is used at some stage to separate sample molecules and/or ions from the solvent liquid that carries them into the source of the mass spectrometer. Less volatile but thermally stable compounds can be thermally vaporised in the direct inlet probe (DIP) situated close to the ionising molecular beam. This DIP is standard equipment on most instruments an El spectrum results. Techniques that extend the utility of mass spectrometry to the least volatile and more labile organic molecules include FD, EHD, surface ionisation (SIMS, FAB) and matrix-assisted laser desorption (MALD) as the last... 

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. 

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