Minimum energy path spectroscopy

In order to define how the nuclei move as a reaction progresses from reactants to transition structure to products, one must choose a definition of how a reaction occurs. There are two such definitions in common use. One definition is the minimum energy path (MEP), which defines a reaction coordinate in which the absolute minimum amount of energy is necessary to reach each point on the coordinate. A second definition is a dynamical description of how molecules undergo intramolecular vibrational redistribution until the vibrational motion occurs in a direction that leads to a reaction. The MEP definition is an intuitive description of the reaction steps. The dynamical description more closely describes the true behavior molecules as seen with femtosecond spectroscopy. 

In the chapter on reaction rates, it was pointed out that the perfect description of a reaction would be a statistical average of all possible paths rather than just the minimum energy path. Furthermore, femtosecond spectroscopy experiments show that molecules vibrate in many dilferent directions until an energetically accessible reaction path is found. In order to examine these ideas computationally, the entire potential energy surface (PES) or an approximation to it must be computed. A PES is either a table of data or an analytic function, which gives the energy for any location of the nuclei comprising a chemical system. 

Photoemission spectroscopy involves measurement of the energy distribution of electrons emitted from a solid under irradiation with mono-energetic photons. In-house experiments are usually performed with He gas discharge lamps which generate vacuum UV photons at 21.2 eV (He la radiation) or 40.8 eV (He Ila radiation ) or with Mg Ka (hv=1284.6 eV) or A1 Ka (hv=1486.6eV) soft X-ray sources. UV photoemission is restricted to the study of valence and conduction band states, but XPS allows in addition the study of core levels. Alternatively photoemission experiments may be performed at national synchrotron radiation facilities. With suitable choice of monochromators it is possible to cover the complete photon energy range from about 5 eV upward to in excess of 1000 eV. The surface sensitivity of photoemission derives from the relatively short inelastic mean free path of electrons in solids, which reaches a minimum of about 5A for electron energies of the order 50-100 eV. 

The information depth of both electron spectroscopies is determined by the inelastic mean-free path of the emitted electrons, which depends on the kinetic energy of the electron in the solid matrix. This dependence is known and has a minimum of about two atomic layers around 25 eV (53). The electron mean-free path is typically larger in oxides than in metals at equal energy, and it is particularly large for zeolites because of their low density. Together with reported ionization cross sections and in the case of AES, Auger decay probabilities, quantitative surface analysis is possible. Compilations of standard spectra are available from which peak energies and sensitivity factors can be obtained (53). 

---