Radiation, resonance

An important development in microwave/optical double resonance, called microwave/optical polarisation spectroscopy, was described by Ernst and Torring [42], The principles of this technique are illustrated in figure 11.22. A linearly polarised probe beam from a tunable laser is sent through the gas sample and a nearly crossed linear polariser, before its final detection. Polarised microwave radiation resonant with a rotational transition in the gas sample is introduced via a microwave horn as shown, and resonant absorption results in a partial change in polarisation of... 

Figure 1 illustrates how a pump laser radiation resonance to the transition 1 4 (Bh Pe) transfers an electron from state Ph in the valence band to state Pe in the conduction band. The electron transfer creates the inversion population for both intraband transition 4 3 in the conduction band and intraband transition 2 1 in the valence band. Although the number of electrons on Ph level is bigger then that on Sii level, we use the term inversion population because absorption of photons on the transition 1 2 is absent since all states on the level Ph are occupied. 

In an ensemble of two-level atoms, all of them may be initially prepared in state 0, and driven by a long pulse of radiation resonant with the transition 0 -> 1. When we neglect relaxation, for simplicity, the excitation probability for each atom... 

The related method of atomic resonance fluorescence—the measurement of intensity of fluorescence excited by absorption of resonance radiation—has several advantages over resonance absorption for kinetic studies of reactions of ground state atoms. When the usual strongly self-reversed microwave discharge lamps are used as the sources of resonance radiation, resonance fluorescence is much more sensitive than resonance absorption. The following lower limits of concentration detectable by resonance fluorescence have been found in this laboratory for particular instrumental conditions [Cl] 5 x 10 g atomcm ... 

FLN techniques produce their most dramatic effects when a metastable electronic transition is pumped and the radiation resonant to the laser excitation is observed. Various additional sources of broadening remain in the FLN spectra if other excitation-emission schemes are followed. Thus, for example, httle narrow-... 

How can y-radiation resonance absorption be seen and measured Assume that the emitter and absorber materials are quite similar and are in the same state. The maximum value of resonance absorption must be observed, when emitter and absorber are motionless (y=0) (eq. 8.3.2). When one begins to move, e.g., the emitter regarding the absorber, this resonance absorption is destroyed and the experiment reveals an absorption curve a very small relative velocity is needed to separate the spectral lines (emitted and absorbed). 

Mosshauer effect The resonance fluorescence by y-radiation of an atomic nucleus, returning from an excited state to the ground state. The resonance energy is characteristic of the chemical environment of the nucleus and Mossbauer spectroscopy may be used to yield information about this chemical environment. Used particularly in the study of Fe. Sn and Sb compounds. 

The unique feature in spontaneous Raman spectroscopy (SR) is that field 2 is not an incident field but (at room temperature and at optical frequencies) it is resonantly drawn into action from the zero-point field of the ubiquitous blackbody (bb) radiation. Its active frequency is spontaneously selected (from the infinite colours available in the blackbody) by the resonance with the Raman transition at co - 0I2 r material. The effective bb field mtensity may be obtained from its energy density per unit circular frequency, the... 

Unlike the typical laser source, the zero-point blackbody field is spectrally white , providing all colours, CO2, that seek out all co - CO2 = coj resonances available in a given sample. Thus all possible Raman lines can be seen with a single incident source at tOp Such multiplex capability is now found in the Class II spectroscopies where broadband excitation is obtained either by using modeless lasers, or a femtosecond pulse, which on first principles must be spectrally broad [32]. Another distinction between a coherent laser source and the blackbody radiation is that the zero-point field is spatially isotropic. By perfonuing the simple wavevector algebra for SR, we find that the scattered radiation is isotropic as well. This concept of spatial incoherence will be used to explain a certain stimulated Raman scattering event in a subsequent section. 

Melinger J S and Albrecht A C 1986 Theory of time- and frequency-resolved resonance secondary radiation from a three-level system J. Chem. Phys. 84 1247-58... 

Waveguides are coimnonly used to transmit microwaves from the source to the resonator and subsequently to the receiver. For not-too-high-frequency radiation (<10 GHz) low-loss MW transmission can also be achieved usmg strip-lines and coaxial cables. At the output of a klystron an isolator is often used to prevent back-reflected microwaves to perturb the on-resonant klystron mode. An isolator is a microwave-ferrite device that pemiits the transmission of microwaves in one direction and strongly attenuates their propagation in the other direction. The prmciple of this device involves the Faraday effect, that is, the rotation of the polarization... 

When the applied magnetic field is swept to bring the sample into resonance, MW power is absorbed by the sample. This changes the matching of the cavity to the waveguide and some power is now reflected and passes via the circulator to the detector. This reflected radiation is thus the EPR signal. 

In the previous chapters experiments have been discussed in which one frequency is applied to excite and detect an EPR transition. In multiple resonance experiments two or more radiation fields are used to induce different transitions simultaneously [19, 20, 21, 22 and 23], These experiments represent elaborations of standard CW and pulsed EPR spectroscopy, and are often carried out to complement conventional EPR studies, or to refine the infonnation which can in principle be obtained from them. 

The Goeppert-Mayer two- (or multi-) photon absorption, mechanism (ii), may look similar, but it involves intennediate levels far from resonance with one-photon absorption. A third, quasi-resonant stepwise mechanism (iii), proceeds via smgle- photon excitation steps involvmg near-resonant intennediate levels. Finally, in mechanism (iv), there is the stepwise multiphoton absorption of incoherent radiation from themial light sources or broad-band statistical multimode lasers. In principle, all of these processes and their combinations play a role in the multiphoton excitation of atoms and molecules, but one can broadly... 

B) The multiphoton excitation of electronic levels of atoms and molecules with visible or UV radiation generally leads to ionization. The mechanism is generally a combination of direct, Goeppert-Mayer, and quasi-resonant stepwise processes. Since ionization often requires only two or tln-ee photons, this type of multiphoton excitation is used for spectroscopic purposes in combination with mass-spectrometric detection of ions. 

B2.5.351 after multiphoton excitation via the CF stretching vibration at 1070 cm. More than 17 photons are needed to break the C-I bond, a typical value in IR laser chemistry. Contributions from direct absorption (i) are insignificant, so that the process almost exclusively follows the quasi-resonant mechanism (iii), which can be treated by generalized first-order kinetics. As an example, figure B2.5.15 illustrates the fonnation of I atoms (upper trace) during excitation with the pulse sequence of a mode-coupled CO2 laser (lower trace). In addition to the mtensity, /, the fluence, F, of radiation is a very important parameter in IR laser chemistry (and more generally in nuiltiphoton excitation) ... 

In contrast to the ionization of C q after vibrational excitation, typical multiphoton ionization proceeds via the excitation of higher electronic levels. In principle, multiphoton ionization can either be used to generate ions and to study their reactions, or as a sensitive detection technique for atoms, molecules, and radicals in reaction kinetics. The second application is more common. In most cases of excitation with visible or UV laser radiation, a few photons are enough to reach or exceed the ionization limit. A particularly important teclmique is resonantly enlianced multiphoton ionization (REMPI), which exploits the resonance of monocluomatic laser radiation with one or several intennediate levels (in one-photon or in multiphoton processes). The mechanisms are distinguished according to the number of photons leading to the resonant intennediate levels and to tire final level, as illustrated in figure B2.5.16. Several lasers of different frequencies may be combined. 

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... 

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