Least motion principle, definition

It should be noted that throughout this chapter, the words model and simulation are used to mean a procedure that solves mathematical equations to represent reality. This may be a less common definition of the word model for some readers. However, since the equations governing aerosol and fluid motion are well established and represent reality exactly, such models have the ability to represent reality exactly, at least in principle. 

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... 

Following Atkins [68], the propagation of particles follows a path dictated by Newton s laws, equivalent to Hamilton s principle, that particles select paths between two points such that the action associated with the path is a minimum. Therefore, Fermat s principle for light propagation is Hamilton s principle for particles. The formal definition of action is an integral identical in structure with the phase length in physical optics. Therefore, particles are associated with wave motion, the wave-particle dualism. Hamilton s principle of least... 

---