Resonant absorption

The original method employed was to scan eitiier the frequency of the exciting oscillator or to scan the applied magnetic field until resonant absorption occiined. Flowever, compared to simultaneous excitation of a wide range of frequencies by a short RF pulse, the scanned approach is a very time-inefficient way of recording the spectrum. Flence, with the advent of computers that could be dedicated to spectrometers and efficient Fourier transfomi (FT) algoritluns, pulsed FT NMR became the nomial mode of operation. 

Bloembergen N, Purcell E M and Pound R V 1948 Relaxation effects In nuclear magnetic resonance absorption Phys. Rev. 73 679-712... 

Application of an oscillating magnetic field at the resonance frequency induces transitions in both directions between the two levels of the spin system. The rate of the induced transitions depends on the MW power which is proportional to the square of oi = (the amplitude of the oscillating magnetic field) (see equation (bl.15.7)) and also depends on the number of spins in each level. Since the probabilities of upward ( P) a)) and downward ( a) p)) transitions are equal, resonance absorption can only be detected when there is a population difference between the two spin levels. This is the case at thennal equilibrium where there is a slight excess of spins in the energetically lower p)-state. The relative population of the two-level system in thennal equilibrium is given by the Boltzmaim distribution... 

In the earlier treatment we reached the conclusion that resonance absorption occurs at the Larmor precessional frequency, a conclusion implying that the absorption line has infinitesimal width. Actually NMR absorption bands have finite widths for several reasons, one of which is spin-lattice relaxation. According to the Heisenberg uncertainty principle, which can be stated... 

Moderately slow exchange. The state lifetime is 2t we ask how the absorption band is affected as this becomes smaller. The uncertainty principle argument given earlier is applicable here lifetime broadening will occur as the state lifetime decreases. Thus, we expect resonance absorption at (or near) frequencies Va nnd Vb but the bands will be broader than in the very slow exchange limit. Equation (4-68) is applicable in this regime. 

Revised structures have been proposed for these compounds. The brownish-yellow acid obtained with maleic anhydride has been shown by ultraviolet, infrared, and nuclear magnetic resonance absorption measurements and oxidative degradation to have the tricyclic structure... 

Quadrupole, effects, 25 moment, 188 resonance absorption, 190 Quasi-chemical theory, 122, 123, 128, 137... 

The intensity of the EPR resonance absorption is a measure of the number of paramagnetic centres present [346], while the type of line observed and the measured g factor are indications of the interactions of the paramagnetic particles and of their distribution within the matrix. Such spectra are much more sensitive to changes in crystal field and atomic orientations than X-ray diffraction and are not dependent upon crystallinity [347]. The nature of the paramagnetic particles may be discerned from the superfine structure of the spectrum. 

The 1H NMR spectra of the epimeric cyclohexanols in DMSO reveal that the hydroxyl proton in the axial alcohol shows a resonance absorption at a higher field than in the equatorial one, indicating that the conformational effect of the hydrogen bond influences the XH NMR chemical shifts128. 

Kubo R. Note on the stochastic theory of resonance absorption, J. Phys. Soc. Japan 9, 935-46 (1954). 

Experiments on the sky. Two experiments have been carried out at the sky, using two laser installations built for the American and French programmes for Uranium isotope separation, respectively AVLIS at the Lawrence Livermore Nat l Lab (California) in 1996 and SILVA at CEA/Pierrelatte (Southern France) in 1999. The average power was high pa 2 x 175 W, with a pulse repetition rate of 12.9 and 4.3 kHz, a pulse width of 40 ns and a spectral width of 1 and 3 GHz. Polarization was linear. The return flux was < 5 10 photons/m /s (Foy et al., 2000). Thus incoherent two-photon resonant absorption works, with a behavior consistent with models. But we do need lower powers at observatories ... 

Fig. 2. A plot of the absorbances of typical lines attributed to Vj, relative to that of a V resonance absorption as a function of the V metal deposition rate at constant Ar deposition rate (108).

Fig. 16. The UV-visible spectra of Ag,jj /Kr mixtures (Ag/Kr = l/10 )at 10-12K (A) After a 30-min irradiation centered at the atomic resonance absorption lines. (B ) The outcome of a 10-min, 423-nm Agj irradiation, showing major decay of the bands associated with Ag, (indicated by arrows) and the appearance of two new bands near 450 nm. (C) The result of a 5-min, 25K bulk thermal annealing period, showing regeneration of the original Ag3 spectrum eind loss of the new band near 445 nm USD.

A more selective method for aggregation of metal atoms in an inert matrix is cryophotoaggregation e.g., atomic Ag is irradiated in an Ar matrix with UV at the atomic resonance absorption of the entrapped Ag atoms, i.e., 315 nm. After ca. 1 h irradiation, the UV spectrum of the matrix shows that the concentration of atomic Ag has decreased and that new absorptions corresponding to Agj and Ag, have appeared. Aggregates up to Ag, can be prepared in this way, and clusters of CU2 and Cu, in a matrix of Ar may be obtained similarly. 

The Mossbauer effect, discovered by Rudolf L. Mossbauer in 1957, can in short be described as the recoil-free emission and resonant absorption of gamma radiation by nuclei. In the case of iron, the source consists of Co, which decays with a half-life of 270 days to an excited state of Fe (natural abundance in iron 2%). The latter, in turn, decays rapidly to the first excited state of this isotope. The final decay generates a 14.4 keV photon and a very narrow natural linewidth of the order of nano eV. 

Significantly different ratios for the resonant absorption area. A, of the two doublets have been obtained for FePc preadsorbed at high loadings (> 15Z) upon changing the available surface area of the carbon. Specifically, a higher value of A2/Aj was found... 

Fig. 2.1 Nuclear resonance absorption of y-rays (Mossbauer effect) for nuclei with Z protons and N neutrons. The top left part shows the population of the excited state of the emitter by the radioactive decay of a mother isotope (Z, N ) via a- or P-emission, or K-capture (depending on the isotope). The right part shows the de-excitation of the absorber by re-emission of a y-photon or by radiationless emission of a conversion electron (thin arrows labeled y and e , respectively)...

Resonant y-ray absorption is directly connected with nuclear resonance fluorescence. This is the re-emission of a (second) y-ray from the excited state of the absorber nucleus after resonance absorption. The transition back to the ground state occurs with the same mean lifetime t by the emission of a y-ray in an arbitrary direction, or by energy transfer from the nucleus to the K-shell via internal conversion and the ejection of conversion electrons (see footnote 1). Nuclear resonance fluorescence was the basis for the experiments that finally led to R. L. Mossbauer s discovery of nuclear y-resonance in ir ([1-3] in Chap. 1) and is the basis of Mossbauer experiments with synchrotron radiation which can be used instead of y-radiation from classical sources (see Chap. 9). 

Hence, nuclear resonance absorption of y-photons (the Mbssbauer effect) is not possible between free atoms (at rest) because of the energy loss by recoil. The deficiency in y-energy is two times the recoil energy, 2Er, which in the case of Fe is about 10 times larger than the natural line width F of the nuclear levels involved (Fig. 2.4). 

Fig. 2.4 Energy separation of y-emission and absorption lines caused by recoil of resting free nuclei (2 r lO T, note the three separate sections of the energy scale). Since there is virtually no overlap between emission and absorption line, resonant absorption is not possible...

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