Pseudo-resonances

Electron donation by an alkyl group can be considered an inductive or a pseudo-resonance effect (See hyper conjugation). Hyperconjugation cannot be demonstrated with second-order resonance structures. 

Figure Bl.16.9. Background-free, pseudo-steady-state CIDNP spectra observed in the photoreaction of triethylamine with different sensitizers ((a), antliraquinone (b), xanthone, CIDNP net effect (c), xanthone, CIDNP multiplet effect, amplitudes multiplied by 1.75 relative to the centre trace) in acetonitrile-d3. The stmctiiral formulae of the most important products bearing polarizations (1, regenerated starting material 2, N,N-diethylvinylamine 3, combination product of amine and sensitizer) are given at the top R denotes the sensitizer moiety. The polarized resonances of these products are assigned in the spectra. Reprinted from [21].

Quasi-resonant converters are a separate class of switching power supplies that tune the ac power waveforms to reduce or eliminate the switching loss within the supply. This is done by placing resonant tank circuits within the ac current paths to create pseudo-sinusoidal voltage or current waveforms. Because the tank circuits have one resonant frequency, the method of control needs to be modified to a variable frequency control where the resonant period is fixed and the control varies the period of the non-resonant period. The quasi-resonant converters usually operate in the 300 kHz to 2 MHz frequency range. 

By the use of nuclear magnetic double (and triple) resonance, the configuration (34) of pseudo-talose was established, confirming chemical evidence, and the sidechain-equatorial conformation (38) was also... 

Perhaps the most detailed studies of both the isotropic and anisotropic exchange interactions have been made for InP, where the anisotropic (pseudo-dipolar) part of the 31P-115In exchange coupling was shown to reduce the measured 31P second moments from theoretical values calculated from dipolar couplings alone [255, 256]. Double and triple resonance 31P MAS-NMR experiments have also provided much information as a result of the existence of the two nearly identical isotopes of... 

Problem What is the critical weighting i/>dip of the alternative dipolar amide resonance structure in (5.102) that would reverse the preference for pseudo-c/s over pseudo-trans geometry at Cal What are the corresponding bond lengths Rco and Rcn at this critical resonance weighting ... 

The reactant R2 can also be considered to be a solvent molecule. The global kinetics become pseudo first order in Rl. For a SNl mechanism, the bond breaking in R1 can be solvent assisted in the sense that the ionic fluctuation state is stabilized by solvent polarization effects and the probability of having an interconversion via heterolytic decomposition is facilitated by the solvent. This is actually found when external and/or reaction field effects are introduced in the quantum chemical calculation of the energy of such species [2]. The kinetics, however, may depend on the process moving the system from the contact ionic-pair to a solvent-separated ionic pair, but the interconversion step takes place inside the contact ion-pair following the quantum mechanical mechanism described in section 4.1. Solvation then should ensure quantum resonance conditions. 

Several modifications have been proposed for the basic HNN-COSY experiment. For example, frequency separations between amino and aromatic 15N resonances are typically in the range 100-130 ppm and therefore much larger than between imino 15N donor and aromatic 15N acceptor resonances. As has been pointed out by Majumdar and coworkers [33], such 15N frequency separations are too large to be covered effectively by the non-selective 15N pulses of the homonuclear HNN-COSY. They therefore designed a pseudo-heteronuclear H(N)N-COSY experiment, where selective 15N pulses excite the amino and aromatic 15N resonances separately to yield excellent sensitivity [33]. An inconvenience of this experiment is that the resonances corresponding to the amino 15N nuclei are not detected, and a separate spin-echo difference experiment was used to quantify the h2/NN values. A slightly improved version of this pseudo-heteronuclear H(N)N-COSY [35] remedies this problem by the use of phase-coherent 15N pulses such that both amino and aromatic 15N resonances can be detected in a single experiment. 

The resonance structures 65 suggest that the pseudo-meta and pseudo-geminal positions are the preferred sites for substitution however, it has been observed (e.g. in the bromination and acetylation of 4-bromo[2.2]paracyclophane (67)) that there is predominant formation of pseudo-ortho and pseudo-para products 8 3b>8 5> (see Table 3) ... 

In addition to the acoustical modes and MSo, we observe in the first half of the Brillouin zone a weak optical mode MS7 at 19-20 me V. This particular mode has also been observed by Stroscio et with electron energy loss spectrocopy. According to Persson et the surface phonon density of states along the FX-direction is a region of depleted density of states, which they call pseudo band gap, inside which the resonance mode MS7 peals of. This behavior is explained in Fig. 16 (a) top view of a (110) surface (b) and (c) schematic plot of Ae structure of the layers in a plane normal to the (110) surface and containing the (110) and (100) directions, respectively. Along the (110) direction each bulk atom has six nearest neighbors in a lattice plane, while in the (100) direction it has only four. As exemplified in Fig. 17, where inelastic... 

FIGURE 5.8 (a) Typical decay of resonance fluorescence from atomic chlorine in the presence of CH3SCH3 (8.6 x 1013 molecules cm 3) at 297 K and in 50 Torr N2 as the carrier gas (adapted from Stickel et al., 1992). (b) Typical pseudo-first-order plot of slopes of plots such as those in part (a) against the initial concentration of CH3SCH3 (adapted from Stickel et al., 1992). 

A variety of pulsed techniques are particularly useful for kinetic experiments (Mclver and Dunbar, 1971 McMahon and Beauchamp, 1972 Mclver, 1978). In these experiments, ions are initially produced by pulsing the electron beam for a few milliseconds. A suitable combination of magnetic and electric fields is then used to store the ions for a variable period of time, after which the detection system is switched on to resonance to measure the abundance of a given ionic species. These techniques allow the monitoring of ion concentration as a function of reaction time. Since the neutrals are in large excess with respect to the ions, a pseudo first-order rate constant can be obtained in a straightforward fashion from these data. The calculation of the rate constant must nevertheless make proper allowance for the fact that ion losses in the icr cell are not negligible. 

With modern Bruker spectrometers the selective ID NOE experiment is usually performed in a pseudo 2D mode. The raw data is obtained as a 2D matrix with the individual rows (FIDs) corresponding to the different decoupler frequencies used for the selective perturbation plus one row where the decoupler frequency is set well away from any resonance line (reference FID). Consequently this 2D data matrix must first be decomposed into the individual 1D FIDs before the difference FIDs can be calculated. 

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