Motion electronic/nuclear, distinguishing

In spectroscopy we may distinguish two types of process, adiabatic and vertical. Adiabatic excitation energies are by definition thermodynamic ones, and they are usually further defined to refer to at 0° K. In practice, at least for electronic spectroscopy, one is more likely to observe vertical processes, because of the Franck-Condon principle. The simplest principle for understandings solvation effects on vertical electronic transitions is the two-response-time model in which the solvent is assumed to have a fast response time associated with electronic polarization and a slow response time associated with translational, librational, and vibrational motions of the nuclei.92 One assumes that electronic excitation is slow compared with electronic response but fast compared with nuclear response. The latter assumption is quite reasonable, but the former is questionable since the time scale of electronic excitation is quite comparable to solvent electronic polarization (consider, e.g., the excitation of a 4.5 eV n — n carbonyl transition in a solvent whose frequency response is centered at 10 eV the corresponding time scales are 10 15 s and 2 x 10 15 s respectively). A theory that takes account of the similarity of these time scales would be very difficult, involving explicit electron correlation between the solute and the macroscopic solvent. One can, however, treat the limit where the solvent electronic response is fast compared to solute electronic transitions this is called the direct reaction field (DRF). 49,93 The accurate answer must lie somewhere between the SCRF and DRF limits 94 nevertheless one can obtain very useful results with a two-time-scale version of the more manageable SCRF limit, as illustrated by a very successful recent treatment... 

A meaningful comparison of kinetic data obtained in different biological systems should be based on the determination of the respective contributions of the nuclear and electronic factors. The most direct method of separating these contributions consists in the measurement of the temperature dependence of the rate over the widest available range. In the following, we distinguish between experiments performed at room temperature, which are usually interpreted by assuming that all the nuclear motions coupled to the transfer may be described classically, and experiments performed at lower temperature, in which the quantified character of particular vibrational modes may appear. 

In discussing molecular systems which must be described in terms of more than one potential surface, it is desirable to have a clear definition of the variously used term crossing. It is also important to distinguish between (a) interaction of potential surfaces, and (b) transitions from one adiabatic surface to another induced by coupling between nuclear and electronic motions (failure of the Bom-Oppenheimer approximation). 

In chemical dynamics, one can distinguish two qualitatively different types of processes electron transfer and reactions involving bond rearrangement the latter involve heavy-particle (proton or heavier) motion in the formal reaction coordinate. The zero-order model for the electron transfer case is pre-organization of the nuclear coordinates (often predominantly the solvent nuclear coordinates) followed by pure electronic motion corresponding to a transition between diabatic electronic states. The zero-order model for the second type of process is transition state theory (or, preferably, variational transition state theory ) in the lowest adiabatic electronic state (i.e., on the lowest-energy Bom-Oppenheimer potential energy surface). 

Care must be exercised to distinguish the concept of adiabatic Floquet dynamics introduced here, which refers to an adiabatic time-evolution, or to the slow variations of the Floquet basis with time, from the concept of adiabatic representation defined in the previous section, which refers to the slow variations of the electronic Hamiltonian (Floquet or not) with respect to nuclear motions (i.e., the noncommutativity of the electronic Hamiltonian Hei and the nuclear KE operator Tjv). Where confusion is possible and to be avoided, we shall refer to this concept of adiabaticity related to the BO approximation as the R-adiabaticity, while adiabaticity in actual time evolution will be termed t-adiabaticity. Non-adiabatic effects in time evolution are due to a fast variation of the (Floquet) Hamiltonian with time, causing Floquet states to change rapidly in time, to the extent that in going from one time slice to another, a resonance may be projected onto many new resonances as well as diffusion (continuum) states [40], and the Floquet analysis breaks down completely. We will see in Section 5 how one can take advantage of such effects to image nuclear motions by an ultrafast pump-probe process. 

Crystallographic studies are problematic because the hydride is such a poor scatterer of X rays. Hydrides may not be detected or may not be distinguishable with certainty from random electron density maxima in the neighborhood of die metal. Since X rays are scattered by electron density, not by the atomic nuclei, it is the M—H bonding electrons at are detected the.se lie between the two nuclei, so that X-ray methods systematically underestimate the true M—H inter-nuclear distance by approximately O.I A. The best data for detecting hydrides are obtained at low temperatures (to reduce thermal motion) and at low angles... 

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