Perturbation, high-field

HIGH FIELD PERTURBATION AND CHEMICAL RELAXATION OF 2,4,6-TRICHLOROPHENOL AND TRIETHYLAMINE MIXTURES IN CYCLOHEXANE... 

In the high-field limit (F > 1 atomic unit meaning that it is greater than the binding potential) the smoothed Coulomb potential in Eq. (2) can be treated as a perturbation on the regular, classical motion of a free electron in an oscillating field. So, let us first consider the Hamiltonian for the one-dimensional motion of a free electron in the... 

Fig. 6.17 Tunnelling and saddle point ionization in Li. (a) Experimental map of the energy levels of Li m = 1 states in a static field. The horizontal peaks arise from ions collected after laser excitation. Energy is measured relative to the one-electron ionization limit. Disappearance of a level with increasing field indicates that the ionization rates exceed 3 x 105 s 1. The dotted line is the classical ionization limit given by Eqs. (6.35) and (6.36). One state has been emphasized by shading, (b) Energy levels for H (n = 18-20, m = 1) according to fourth order perturbation theory. Levels from nearby terms are omitted for clarity. Symbols used to denote the ionization rate are defined in the key. The tick mark indicates the field where the ionization rate equals the spontaneous radiative rate, (c) Experimental map as in (a) except that the collection method is sensitive only to states whose ionization rate exceeds 3 x 105 s-1. At high fields, the levels broaden into the continuum in agreement with tunnelling theory for H (from ref. 32).

Several chapters of this book show how magnetic field effects, as well as CIDEP and CIDNP spectral patterns, can be used to solve chemical problems. It should be noted that the study of how applied magnetic fields perturb chemical reactivity is a topic that is highly relevant to biological processes involving radical pairs, for example, photosynthesis. ... 

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