Time-resolved photoelectron spectroscopy applications

In addition to the natural improvements expected in the accuracy of the measurements, and the increased scope in the types of systems examined, new techniques go beyond the issue of thermochemistry to allow for very detailed studies of reaction dynamics. The investigation by Zewail and co-workers of the reactivity of planar COT" on the femtosecond time scale is likely only the beginning. Time-resolved photoelectron spectroscopy, for example, has recently been used to map the potential energy surfaces for the dissociation of simple ions IBr and l2. " Although applications in the field of organic reactive molecules are likely far off, they are now possible. 

In conclusion, the realm for femtosecond time-resolved photoelectron spectroscopy to cover has been extended such that it is applicable to simultaneous electronic and vibrational dynamics in molecules. 

Structure, then the time-resolved photoelectron spectra [20, 21] could reveal signatures of two different intermediate structures, representing two different pathways on the PES. Transient absorption spectroscopy and other femtosecond time-resolved techniques may also be applicable to this problem. 

To illustrate the practical application of the theoretical formalism, we have discussed several representative examples that demonstrate the potential of femtosecond time-resolved spectroscopy. Since typically only a few degrees of freedom (say, 2-4) are involved in the ultrafast photodynamics via a conical intersection, explicit simulations of spectroscopic experiments for polyatomic molecules are nowadays possible on a routine basis. As an example of a state-of-the-art simulation of a femtosecond experiment on a polyatomic system, we have presented first-principles calculations of the time-resolved photoelectron spectra of pyrazine. Although in this case the interpretation was found to be quite complicated, the investigations nevertheless demonstrated the considerable potential of a joint experimental/theoretical study of the dynamics at conical intersections. Employing... 

The operation and application of streak cameras in fluorescence lifetime spectroscopy has been reviewed previously (see, e.g., Refs. 91 and 92). Streak cameras are useful in 2-D time-resolved imaging applications such as microscopy or multiwavelength array fluorometry. The operating principle is based on converting an optical pulse into a photoelectron pulse and spatially dispersing the electron image on a phosphor by means of a synchronized deflection voltage across two plates. 

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