3 resultados para Hausdorff Distance
em CaltechTHESIS
Resumo:
The rate of electron transport between distant sites was studied. The rate depends crucially on the chemical details of the donor, acceptor, and surrounding medium. These reactions involve electron tunneling through the intervening medium and are, therefore, profoundly influenced by the geometry and energetics of the intervening molecules. The dependence of rate on distance was considered for several rigid donor-acceptor "linkers" of experimental importance. Interpretation of existing experiments and predictions for new experiments were made.
The electronic and nuclear motion in molecules is correlated. A Born-Oppenheimer separation is usually employed in quantum chemistry to separate this motion. Long distance electron transfer rate calculations require the total donor wave function when the electron is very far from its binding nuclei. The Born-Oppenheimer wave functions at large electronic distance are shown to be qualitatively wrong. A model which correctly treats the coupling was proposed. The distance and energy dependence of the electron transfer rate was determined for such a model.
Resumo:
A series of meso-phenyloctamethylporphyrins covalently bonded at the 4'phenyl position to quinones via rigid bicyclo[2.2.2]octane spacers were synthesized for the study of the dependence of electron transfer reaction rate on solvent, distance, temperature, and energy gap. A general and convergent synthesis was developed based on the condensation of ac-biladienes with masked quinonespacer-benzaldehydes. From picosecond fluorescence spectroscopy emission lifetimes were measured in seven solvents of varying polarity. Rate constants were determined to vary from 5.0x109sec-1 in N,N-dimethylformamide to 1.15x1010 Sec-1 in benzene, and were observed to rise at most by about a factor of three with decreasing solvent polarity. Experiments at low temperature in 2-MTHF glass (77K) revealed fast, nearly temperature-independent electron transfer characterized by non-exponential fluorescence decays, in contrast to monophasic behavior in fluid solution at 298K. This example evidently represents the first photosynthetic model system not based on proteins to display nearly temperature-independent electron transfer at high temperatures (nuclear tunneling). Low temperatures appear to freeze out the rotational motion of the chromophores, and the observed nonexponential fluorescence decays may be explained as a result of electron transfer from an ensemble of rotational conformations. The nonexponentiality demonstrates the sensitivity of the electron transfer rate to the precise magnitude of the electronic matrix element, which supports the expectation that electron transfer is nonadiabatic in this system. The addition of a second bicyclooctane moiety (15 Å vs. 18 Å edge-to-edge between porphyrin and quinone) reduces the transfer rate by at least a factor of 500-1500. Porphyrinquinones with variously substituted quinones allowed an examination of the dependence of the electron transfer rate constant κET on reaction driving force. The classical trend of increasing rate versus increasing exothermicity occurs from 0.7 eV≤ |ΔG0'(R)| ≤ 1.0 eV until a maximum is reached (κET = 3 x 108 sec-1 rising to 1.15 x 1010 sec-1 in acetonitrile). The rate remains insensitive to ΔG0 for ~ 300 mV from 1.0 eV≤ |ΔG0’(R)| ≤ 1.3 eV, and then slightly decreases in the most exothermic case studied (cyanoquinone, κET = 5 x 109 sec-1).
Resumo:
Let E be a compact subset of the n-dimensional unit cube, 1n, and let C be a collection of convex bodies, all of positive n-dimensional Lebesgue measure, such that C contains bodies with arbitrarily small measure. The dimension of E with respect to the covering class C is defined to be the number
dC(E) = sup(β:Hβ, C(E) > 0),
where Hβ, C is the outer measure
inf(Ʃm(Ci)β:UCi Ↄ E, Ci ϵ C) .
Only the one and two-dimensional cases are studied. Moreover, the covering classes considered are those consisting of intervals and rectangles, parallel to the coordinate axes, and those closed under translations. A covering class is identified with a set of points in the left-open portion, 1’n, of 1n, whose closure intersects 1n - 1’n. For n = 2, the outer measure Hβ, C is adopted in place of the usual:
Inf(Ʃ(diam. (Ci))β: UCi Ↄ E, Ci ϵ C),
for the purpose of studying the influence of the shape of the covering sets on the dimension dC(E).
If E is a closed set in 11, let M(E) be the class of all non-decreasing functions μ(x), supported on E with μ(x) = 0, x ≤ 0 and μ(x) = 1, x ≥ 1. Define for each μ ϵ M(E),
dC(μ) = lim/c → inf/0 log ∆μ(c)/log c , (c ϵ C)
where ∆μ(c) = v/x (μ(x+c) – μ(x)). It is shown that
dC(E) = sup (dC(μ):μ ϵ M(E)).
This notion of dimension is extended to a certain class Ӻ of sub-additive functions, and the problem of studying the behavior of dC(E) as a function of the covering class C is reduced to the study of dC(f) where f ϵ Ӻ. Specifically, the set of points in 11,
(*) {dB(F), dC(f)): f ϵ Ӻ}
is characterized by a comparison of the relative positions of the points of B and C. A region of the form (*) is always closed and doubly-starred with respect to the points (0, 0) and (1, 1). Conversely, given any closed region in 12, doubly-starred with respect to (0, 0) and (1, 1), there are covering classes B and C such that (*) is exactly that region. All of the results are shown to apply to the dimension of closed sets E. Similar results can be obtained when a finite number of covering classes are considered.
In two dimensions, the notion of dimension is extended to the class M, of functions f(x, y), non-decreasing in x and y, supported on 12 with f(x, y) = 0 for x · y = 0 and f(1, 1) = 1, by the formula
dC(f) = lim/s · t → inf/0 log ∆f(s, t)/log s · t , (s, t) ϵ C
where
∆f(s, t) = V/x, y (f(x+s, y+t) – f(x+s, y) – f(x, y+t) + f(x, t)).
A characterization of the equivalence dC1(f) = dC2(f) for all f ϵ M, is given by comparison of the gaps in the sets of products s · t and quotients s/t, (s, t) ϵ Ci (I = 1, 2).