Pulse with selective excitation

Fig. 8. ID ROESY-TOCSY. (a) H spectrum of the oligosaccharide 3 (5 mg/0.5 ml D2O). (b) ID ROESY spectrum of 3 acquired using the pulse sequence of fig. 7(a) with selective excitation of the H-lb proton. Duration of the 270° Gaussian pulse and the spin-lock pulse ( yBi/ K = 2.8 kHz) was 49.2 ms and 0.5 s, respectively. The spin-lock pulse was applied 333.3 Hz downfield from the H-lb resonance. The time used for the frequency change was 3 ms. (c) ID ROESY-TOCSY spectrum acquired using the pulse sequence of fig. 7(c) and the selective ROESY transfer from H-lb followed by a selective TOCSY transfer from H-4c. Parameters for the ROESY part were the same as in (b). A 49.2 ms Gaussian pulse was used at the beginning of the 29.07 ms TOCSY spin lock. 256 scans were accumulated. A partial structure of 3 is given in the inset. Solid and dotted lines represent TOCSY and ROESY...

FIGURE 43. Assignment of the two lines in the 29Si NMR spectmm of methyl 3o, 12a-bis(trimethyl-siloxy)-5/i-cholenate, 37, by selective INEPT. Top trace 29Si INEPT spectmm two middle traces selective INEPT spectra measured with selective excitation of H lines indicated by arrows in the bottom trace with partially assigned ll NMR spectmm (25 mg of the sample in 0.7 ml of CDCI3, H frequency 200 MHz, 29Si frequency 39.7 MHz, 5 mm broad-band probe, selective pulse by DANTE train, r = 70 ms, A = 149 ms). Reproduced with permission of Collection of Czechoslovak Chemical Communications from Reference 304... 

A pulse laser is another excitation source for generating various reactive intermediates efficiently. In the case of pulse lasers, selective excitation of the ground and excited states is easy because laser pulses with various wavelengths can be obtained by harmonic generation with nonlinear crystals. Recent development of a laser utilizing optical parametric oscillation, which emits a variable wavelength, enlarged the scope of study. Thus, two-color two-laser flash photolysis has been adapted to a wide variety of fields [3]. Furthermore, utilization of... 

Fig. 1. Pulse sequences for ID- X, "Y H) polarization transfer experiments. If not stated otherwise, narrow and wide bars denote 90° and 180° hard pulses, narrow and wide ellipsoids 90° and 180° shaped pulses. Essential phase cycles for selection of the polarization transfer signal are given on top of the pulses, if no phase is indicated, pulses are applied along the x-axis A denotes a fixed delay of length (n/(X,Y))" (a) UPT (, 0 = 90°), (b) unrefocused INEPT, (c) unrefocused selective INEPT with soft pulses, (d) INEPT with selective excitation via H, "Y cross-polarization si denote WALTZ-17 spinlock pulse trains which were applied for a period t— (2/( H,Y)) ...

Recent applications of pseudo-triple- and -quadruple resonance techniques have in particular focused on the use of indirect detection schemes to measure heteronuclear couplings with increased sensitivity. The most versatile technique for this purpose proved to be H,"X( "Y) or "Xj HK Y) HMQC experiments which use I -BIRD or bi-selective pulses for selective excitation of transitions of ""Y isotopomers and allow to determine both the magnitude of/("X, Y) and its sign relative to /( H/ B X). Experiments of this type are easily employed to spin systems where /( H/ P,"X) ( H/ B Y) which is frequently the case if "Y is a C nucleus which is directly bound to the detected H or P spin, and have been used in a number of cases to measure couplings between C and rare spins such as 109,111 57pgii2 qj. 18705 196 similar B-BIRD-HSQC experiment has also been applied to the measurement of 7( Si, N) in NH-substituted azasilaboroles. ... 

In Check it 5.3.1.4 the x- and y-profiles of the transverse magnetization for a 270° Gaussian pulse [5.91], a 90° half-GAUSSiAN pulse [5.92] and a 90° Gaussian Pulse Cascade G4 [5.93] are compared. Finally the H spectra of dibromopropionic acid with selective excitation of the proton at 2.85 ppm is simulated for all three shaped pulses. 

In section II.A.2. we discussed how the rf pulse acts on the nuclear spins. We now discuss this topic further and apply the results to several examples having to do with selective excitation. There are many reasons for wanting to perform selective excitation in NMR. Some of them are to simplify complex spectra, to do selective population transfer in order to get the sign of spin-spin coupling, and to study cross relaxation. An important application of what we might call selective de-excitation is a notch in the irradiation pattern to suppress an unwanted resonance such as the solvent peak in a complex proton spectrum. Morris and Freeman (1978) have reviewed many aspects of such experiments. 

This feature can be a problem, but also offers a means of applying selective pulses to excite only some selected resonance lines in a given window defined by the frequency and bandwidth of the RF pulse. Therefore, it is quite common to use pulses with large intensity (named hard pulses) for non-selective irradiation (i.e., excitation of all nuclei irrespective of their particular resonant frequencies) and low-power pulses (named soft pulses) to selective excitation [5],... 

Probably the first suggestion for utilizing the properties of laser light (the high intensity and short duration of radiation pulses) was (Letokhov 1969) to use the vibrationally mediated photodissociation of molecules via an excited repulsive electronic state with noncoherent isotope-selective saturation of the vibrational transition (Fig. 11.2). The isotope-selective two-step photodissociation of molecules consists of pulsed isotope-selective excitation of a vibrational state in the molecules by IR laser radiation and subsequent pulsed photodissociation of the vibrationally excited molecules via an excited electronic state by a UV pulse (Fig. 11.2(a)) before the isotope selectivity of the excitation is lost in collisions. Selective two-step photodissociation of molecules is possible if their excitation is accompanied by a shift of their continuous-wave electronic photoabsorption band. In that case, the molecules of the desired isotopic composition, selectively excited by a laser pulse of frequency uji, can be photodissociated by a second laser pulse of frequency uj2 selected to fall within the region of the shift where the ratio between the absorption coefficients of the excited and unexcited molecules is a maximum (Fig. 11.2(b)). 

Figure 2.28 Ion trap scan function. The sequence of events used to generate a mass spectrum in a typical Paul trap is shown. This sequence is typically repeated many times with the individual spectra summed or averaged to produce the final spectrum. The generic parts of the scan function shown include (1) ion injection and trapping, (2) ion relaxation/cooling, (3) auxiliary excitation for selective ejection/storage of desired ions and (4) mass-selective instability scan. The timing of the resonant excitation function is also indicated two sine waves shown indicate a first pulse for selective excitation and a second pulse for enhancing the mass selective instability scan...

As an example, we mention the detection of iodine atoms in their P3/2 ground state with a 3 + 2 multiphoton ionization process at a laser wavelength of 474.3 run. Excited iodine atoms ( Pi/2) can also be detected selectively as the resonance condition is reached at a different laser wavelength of 477.7 run. As an example, figure B2.5.17 hows REMPI iodine atom detection after IR laser photolysis of CF I. This pump-probe experiment involves two, delayed, laser pulses, with a 200 ns IR photolysis pulse and a 10 ns probe pulse, which detects iodine atoms at different times during and after the photolysis pulse. This experiment illustrates a frindamental problem of product detection by multiphoton ionization with its high intensity, the short-wavelength probe laser radiation alone can photolyse the... 

Another important breaktlirough occurred with the 1974 development by Laubereau et al [24] of tunable ultrafast IR pulse generation. IR excitation is more selective and reliable than SRS, and IR can be used in pump-probe experiments or combined with anti-Stokes Raman probing (IR-Raman method) [16] Ultrashort IR pulses have been used to study simple liquids and solids, complex liquids, glasses, polymers and even biological systems. 

A homonuclear spin-system may be excited with radiofrequency (r.f.) pulses that are so Intense (in the order of p.s), compared to the frequency width of the spectrum, that all resonances are excited essentially uniformly. This is a nonselective excitation. A homonuclear spin-system may also be excited with a relatively weak, r.f. pulse (in the order of ms), in the sense that all components of a given multiplet are inverted at time zero, whereas the other resonances in the spectrum remain essentially unperturbed this is a selective excitation. The r.f. pulse may be single-selective, that is, there is an inversion of one multiplet in the spectrum, or double-selective, triple-selective, and so on, where two, three, or more separate multiplets in the spectrum are inverted simultaneously while the remaining resonances remain unperturbed. 

Gaussian pulses are frequently applied as soft pulses in modern ID, 2D, and 3D NMR experiments. The power in such pulses is adjusted in milliwatts. Hard" pulses, on the other hand, are short-duration pulses (duration in microseconds), with their power adjusted in the 1-100 W range. Figures 1.15 and 1.16 illustrate schematically the excitation profiles of hard and soft pulses, respectively. Readers wishing to know more about the use of shaped pulses for frequency-selective excitation in modern NMR experiments are referred to an excellent review on the subject (Kessler et ai, 1991). 

Figure 7.1 Selective excitation of only one multiplet by a selective pulse transforms a 2D experiment into a ID technique. A selective pulse generates the transverse magnetization. The result is a trace of the corresponding 2D spectrum. (Reprinted from Mag. Reson. Chem. 29, H. Kessler ei al., 527, copyright (1991), with permission from John Wiley and Sons Limited, Baffins Lane, Chichester, Sussex P019 lUD, England.)...

Figure 41. Selective bond breaking of H2O by means of the quadratically chirped pulses with the initial wave packets described in the text. The dynamics of the wavepacket moving on the excited potential energy surface is illustrated by the density, (a) The initail wave packet is the ground vibrational eigen state at the equilibrium position, (b) The initial wave packet has the same shape as that of (a), but shifted to the right, (c) The initail wave packet is at the equilibrium position but with a directed momentum toward x direction. Taken from Ref. [37]. (See color insert.)...

The ability to selectively excite a particular ion (or group of ions) by irradiating the cell with the appropriate radiofrequencies provides a level of flexibility unparalleled in any other mass spectrometer. The amplitude and duration of the applied RF pulse determine the ultimate radius of the ion trajectories. Thus, by simply turning on the appropriate radiofrequency, ions of a single m/z may be ejected from the cyclotron. In this way, a gas-phase separation of analyte from matrix is achieved. At a fixed radius of the ion trajectories the signal is proportional to the number of orbiting ions. Quantitation therefore requires precise RF control. 

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