2 resultados para åk 4-6

em CaltechTHESIS


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In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H2S ˃ C5H6 ˃ CH3NO2 ˃ 1, 4- C5H8 ˃ I ˃ C2H5OH ˃ H2O; cyclo-C7H8 ˃ C2 H5OH; фCH3 ˃ CH3OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C5 H5-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C5H7-, Ia, cyclo-C7H7-) ˂ 377 kcal/mole PA(фCH2-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: Ea = 43.0 kcal/mole, log A = 15.53 and ∆Sǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (Ea = 22.7 kcal/mole; log A = 9.23, ∆Sǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C7H6 isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

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The problem of global optimization of M phase-incoherent signals in N complex dimensions is formulated. Then, by using the geometric approach of Landau and Slepian, conditions for optimality are established for N = 2 and the optimal signal sets are determined for M = 2, 3, 4, 6, and 12.

The method is the following: The signals are assumed to be equally probable and to have equal energy, and thus are represented by points ṡi, i = 1, 2, …, M, on the unit sphere S1 in CN. If Wik is the halfspace determined by ṡi and ṡk and containing ṡi, i.e. Wik = {ṙϵCN:| ≥ | ˂ṙ, ṡk˃|}, then the Ʀi = ∩/k≠i Wik, i = 1, 2, …, M, the maximum likelihood decision regions, partition S1. For additive complex Gaussian noise ṅ and a received signal ṙ = ṡie + ṅ, where ϴ is uniformly distributed over [0, 2π], the probability of correct decoding is PC = 1/πN ∞/ʃ/0 r2N-1e-(r2+1)U(r)dr, where U(r) = 1/M M/Ʃ/i=1 Ʀi ʃ/∩ S1 I0(2r | ˂ṡ, ṡi˃|)dσ(ṡ), and r = ǁṙǁ.

For N = 2, it is proved that U(r) ≤ ʃ/Cα I0(2r|˂ṡ, ṡi˃|)dσ(ṡ) – 2K/M. h(1/2K [Mσ(Cα)-σ(S1)]), where Cα = {ṡϵS1:|˂ṡ, ṡi˃| ≥ α}, K is the total number of boundaries of the net on S1 determined by the decision regions, and h is the strictly increasing strictly convex function of σ(Cα∩W), (where W is a halfspace not containing ṡi), given by h = ʃ/Cα∩W I0 (2r|˂ṡ, ṡi˃|)dσ(ṡ). Conditions for equality are established and these give rise to the globally optimal signal sets for M = 2, 3, 4, 6, and 12.