Probe pulse, time-resolved femtosecond dynamics

D. M. Neumark We are currently carrying out somewhat different femtosecond experiments in which time-resolved photoelectron spectroscopy is used to probe the photodissociation dynamics of negative ions. In these experiments, an anion is photodissociated with a femtosecond laser pulse. After a time delay, the dissociating anion is pho-todetached with a second femtosecond pulse and the resulting photoelectron spectrum is measured. The photoelectron spectrum as a function of delay time provides a detailed probe of the anion photodissociation dynamics. First results have recently been obtained for the photodissociation of I2. 

The coherent motion initiated by an excitation pulse can be monitored by variably delayed, ultrashort probe pulses. Since these pulses may also be shorter in duration than the vibrational period, individual cycles of vibrational oscillation can be time resolved and spectroscopy of vibrationally distorted species (and other unstable species) can be carried out. In the first part of this section, the mechanisms through which femtosecond pulses may initiate and probe coherent lattice and molecular vibrational motion are discussed and illustrated with selected experimental results. Next, experiments in the areas of liquid state molecular dynamics and chemical reaction dynamics are reviewed. These important areas can be addressed incisively by coherent spectroscopy on the time scale of individual molecular collisions or half-collisions. 

Figure 10-7. (a) Absorption spectrum of LPPP. The arrow indicates the spectral position of the excitation pulse in the time-resolved measurements, (b) PL spectrum for LPPP for low excitation pulse energies. (c) Differential transmission spectrum observed in LPPP after photoexcitation with a femtosecond pulse having a pulse energy of 80 nJ at a wavelength of 400 nm. The arrow indicates the spectral position of the probe pulses used for a more detailed investigation of the gain dynamics. 

There are two interesting regimes of time evolution in the probing/detection of dynamical nonequilibrium structures. In the regime of dynamics, the time evolution of atomic positions is detected on its intrinsic timescale, i.e., femtoseconds. Short X-ray pulses - on the timescale of atomic motion - are required in order to follow the dynamics of the chemical bond. In the regime of kinetics, which has to do with the time evolution of populations - and in the context of time-resolved X-ray diffraction -the time evolution in an ensemble average of different interatomic distances or the structural determination of short-lived chemical species is considered. 

The population probabilities Pn t) defined in Eqs. (8)-(13) should not be confused with the population probabilities which have been considered in the extensive earlier literature on radiationless transitions in polyatomic molecules, see Refs. 28 and 29 for reviews. There the population of a single bright (i.e. optically accessible from the electronic ground state) zero-order Born-Oppenheimer (BO) level is considered. Here, in contrast, we define the electronic population as the sum of all vibrational level populations within a given (diabatic or adiabatic) electronic state. These different definitions are adapted to different regimes of time scales of the system dynamics. If nonadiabatic interactions are relatively weak, and radiationless transitions relatively slow, the concept of zero-order BO levels is useful the populations of these levels can be prepared and probed using suitable laser pulses (typically of nanosecond duration). If the nonadiabatic transitions occur on femtosecond time scales, the preparation of individual zero-order BO levels is no longer possible. The total population of an electronic state then becomes the appropriate concept for the interpretation of time-resolved experiments. ° ... 

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