Transition energy ratios

Figure 5. Transition energy ratios v /vi and v%/v% vs. Dq/B for Ti(F) ground state ions...

It should be emphasized that inaccurate values of Dq and B are likely to be derived if the transition energy ratio used is relatively insensitive to Dq/B. For example, considering Figure 3, use of the ratio pz/p2 would be inadvisable in systems where this ratio lies between 1.55 and 1.7. Similarly, the Pz/Pi ratio will provide very inaccurate values if it is less than about 2.2. It is equally true that inaccurate data may be obtained if the energy ratio is highly sensitive to Dq/B because, in this case, a small experimental error will lead to a large change in Dq/B. 

The lowest transition energies of permanganate and dichromate will be ligand to metal charge transfer (LMCT) in nature. From symmetry arguments, it can be shown that the transition described by the 4—> e one-electron transition of a tetrahedral d° complex will have an Aj/Dj ratio of -0.5 (108,109). 

Fig. 2 further illustrates the abruptness of the shape transition. The energy ratio approaches the value of 10/3 characteristic of an axially symmetric rotor for Sr or Zr nuclei... 

Direct solution of the rather complicated equations involved (2f 23) is rather tedious, especially so when the ground state is T and a graphical solution is to be preferred. The method commonly used involves the computation of the ratio of two of the spin-allowed transition energies. 

Beichardt (1965). Molar trmisition energies from the visible spectrum of pyridinium N-phenol betaines in solvents. Dimroth et al. (1963). Molar transition energies from spectrum of l-ethyl-4-methoxycarbonyl pyridinium iodide (Koso rer, 1958). From rates of Sj l solvolyses of alkyl halides and tosylates (Grunwald and Winstein, 1948). From ratio of endo to exo products in the Siels-Alder addition of cyclopentadiene to... 

Let us consider the flux F, per unit of time, through a sphere S of large radius, of the Poynting vector of the field, created by the transition current between two states, of an electron bound in an atom. If we consider the energy E released at each transition, the ratio F/E gives the number of transitions per... 

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