By J. Ulstrup
Molecules in liquid and sturdy media are uncovered to robust inter motion forces from the encompassing medium. The formula of a complete thought of chemical approaches in condensed media is for this reason an problematic activity related to thoughts from a number of parts of the traditional sciences. in the las~ and a part a long time very remarkable effects in the direction of the formula of a 'unified' quantum mechanical thought of such tactics have actually been accomplished, and through the diversity of actual, chemical, and organic tactics which are certainly coated through this framework, the recent thought represents an sufficient replacement to the transition nation thought. the current paintings has a two-fold function. to begin with, to supply a pretty equipped exposition of a few simple points of those advancements. This half emphasizes the elemental similarities among chemical and other forms of radiationless techniques and contains the derivation of crucial fee expressions with out resorting to concerned mathematical concepts. The s- ond significant objective is to demonstrate the 'unified' personality of the speed thought by means of research of a large amount of expe- psychological facts from either 'conventional' kinetics and from such untraditional parts as low-temperature, strongly exothermic, and organic techniques. specific recognition is right here given to these structures for which a classical description is insufficient, and which supply a diagnostic contrast among numerous substitute theoretical approaches.
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Additional resources for Charge Transfer Processes in Condensed Media
55 Moreover, the fictive external field is related to the induced polarization by the equation. c p ... kv n.... 41'1' k .. 29 ) k where the, so far phenomenological, coupling constants eq. 16)) strength) a measure of the c~v (cfr. medium response (oscillator at the paticular frequency W~v. 30) 0 k,v Since U p ... dP- * k'V kv is a real quantity p ... =I 4il -c .... , dP ... kll k'v k'll k" 2 \ ku 1 k\l 0 k ,v c k\l kv amplitudes, P~v' variables. Similarly we ! 31) k,v energy we see that the wave In the expression for the potential bles, jk\, , =I...
Larity should not conceal the fact However, this apparent simi- that the role of the solvent 26 is viewed in In fundamentally different ways in the transition state ascribed solely to tial role the two theories. of the solvent different equilibrium solvation in and transition according theory the to the states. theory induced by deviation tions), and the In contrast, of Marcus from the as noted in electron transfer equilibrium (polarization concept of a transition state is the ini(a), is fluctua- has a different meaning.
26) substantially This is again associated with the fact is itself approximately linear over quite wide intervals of free energy or overpotential. An approximately quadratic dependence of the apparent activation energy on the free energy of reaction is well transfer reactions, in particular known for proton between oxygen- and nitrogen donors and acceptors(19,66,67). Due to the small proton transfer distance, Ao over which a is also here small and the free curvature in the Bronsted plot energy interval is manifested, is therefore correspondingly small.