Chemically induced dynamic intensities

Time-resolved laser flash ESR spectroscopy generates radicals with nonequilibrium spin populations and causes spectra with unusual signal directions and intensities. The signals may show absorption, emission, or both and be enhanced as much as 100-fold. Deviations from Boltzmann intensities, first noted in 1963, are known as chemically induced dynamic electron polarization (CIDEP). Because the splitting pattern of the intermediate remains unaffected, the CIDEP enhancement facilitates the detection of short-lived radicals. A related technique, fluorescence detected magnetic resonance (FDMR) offers improved time resolution and its sensitivity exceeds that of ESR. The FDMR experiment probes short-lived radical ion pairs, which form reaction products in electronically excited states that decay radiatively. ... 

Appropriate modifications of the ESR spectrometer and generation of free radicals by flash photolysis allow time-resolved (TR) ESR spectroscopy [71]. Spectra observed under these conditions are remarkable for their signal directions and intensities. They may be enhanced as much as one hundredfold and may appear in absorption, emission, or in a combination of both modes. These spectra indicate the intermediacy of radicals with substantial deviations from equilibrium populations. Significantly, the splitting pattern characteristic for the spin density distribution of the intermediate remains unaffected thus, the CIDEP (chemically induced dynamic electron polarization) enhancement facilitates the detection of short-lived radicals at low concentrations. 

One of the most important phenomenon, chemically induced dynamic nuclear polarization (CIDNP), deserves more detailed consideration, since it forms the basis of one of the most powerful modem methods for the investigation of the structure and reactivity of short-lived (from nano- to microseconds) paramagnetic precursors of the reaction products. CIDNP manifests itself in the form of unusual line intensities and/or phases of NMR signals observed when the radical reaction takes place directly in the probe of the spectrometer. These anomalous NMR signals—enhanced absorption or emission — are observed within the time of nuclear relaxation of the diamagnetic molecule (from several seconds to several minutes). Later on, the NMR spectrum re-acquires its equilibrium form. 

Finally, it should be pointed out that methods used to study short-lived chemical intermediates in fast thermal reactions may be applicable also to photochemical studies. Radical intermediates, however generated, can be studied by CIDNP (chemically induced dynamic nuclear spin polarization), in which the n.m.r. spectrum of the reaction mixture is recorded during the reaction period. If a substrate is continuously irradiated with ultraviolet/visible light in the cavity of an n.m.r. spectrometer, the resulting n.m.r. spectrum ot the substrale/product mixture exhibits intensity variations as compared with the normal spectrum—intensity enhancement, reduction or even reversal (i.e. emission). Note that the spectrum involved is not... 

Another technique that is specific for radical processes is known as CK)NP, an abbreviation for chemically induced dynamic nuclear polarization The instrumentation required for such studies is an NMR spectrometer. CIDNP is observed as a strong perturbation of the intensity of NMR signals in products formed in certain types of free radical reactions. The variation in intensity results when the normal population of... 

Although EPR signals related to hydrocarbon cations radicals generated by electrochemical oxidation or chemical oxidation can be readily detected, only a few examples have been reported for cation radicals that are produced by irradiation of solutions of electron donors and an acceptor. Because electron spin polarization offers the advantage of detecting transient species via their EPR signal intensities, chemically induced dynamic electron polarization (CIDEP) spectra can give information not only about short-lived radical intermediates... 

NMR spectra of samples in which free radical reactions are taking place may show strongly perturbed intensities for lines belonging to reaction products. This effect is called chemically induced dynamic nuclear polarization or CIDNP. Over the past ten years CIDNP has become an established method for mechanistic investigations of reactions involving short-lived radical intermediates. Several reviews and a mono-... 

While optical methods remain the favored means of analysis in both flash photolysis and pulse radiolysis, other methods of detection have been used with great effectiveness from time to time, including conductivity and ESR spectroscopy. The latter technique, in association with flash photolysis in particular, has led to the observation of ESR signals with anomalous intensities, for example, appearing totally in emission, a phenomenon described as chemically induced dynamic electron polarization or CIDER... 

Another technique for the study of reactions that is highly specific for radical processes is known as CIDNP, an abbreviation for chemically induced dynamic nuclear polarization." The instrumentation required for such studies is a normal NMR spectrometer. CIDNP is observed as a strong perturbation of the intensity of NMR signals in products formed in certain types of free radical reactions. CIDNP is observed when the normal population of nuclear spin states dictated by the Boltzmann distribution is disturbed by the presence of an unpaired electron. The intense magnetic moment associated with an electron causes a polarization of nuclear spin states, which is manifested by enhanced absorption or emission, or both, in the NMR spectrum of the diamagnetic product of a free radical reaction. The technique is less general than EPR spectroscopy because not all free radicals can be expected to exhibit the phenomenon. 

The chemically induced dynamic nuclear polarization (CIDNP) phenomenon, (the occurrence of intense emission and enhanced absorption lines in high-resolution NMR spectra during chemical reactions) has been applied to the study of the photodegradation of poly(methyl isopropenyl ketone) [177]. 

Another burst of activity in free radical research occurred in the 1960s and 1970s, after several reports of anomalous intensities in the EPR spectra of photochemically or radiolytically produced radicals, and in the NMR spectra of the products from free radical reactions in solution." " These so-called chemically induced magnetic spin polarization (CIDNP and CIDEP) phenomena provided a wealth of mechanistic, kinetic, dynamic, and structural information and were a cornerstone of carbon-centered free radical research for the better part of three decades. The umbrella term for this area of research is spin chemistry, which is defined as the chemistry of spin-selective processes. 

An additional piece of information can be obtained by studying a synthetic compound derived from the GFP chromophore (1-28) fluorescing at room temperature. In Fig. 3a we show the chemical structure of the compound that we studied in dioxan solution by pump-probe spectroscopy. If we look at the differential transmission spectra displayed in Fig. 3b, we observed two important features a stimulated emission centered at 508 nm and a huge and broad induced absorption band (580-700 nm). Both contributions appear within our temporal resolution and display a linear behavior as a function of the pump intensity in the low fluences limit (<1 mJ/cm2). We note that the stimulated emission red shifts with two characteristic time-scales (500 fs and 10 ps) as expected in the case of solvation dynamics. We conclude that in the absence of ESPT this chromophore has the same qualitative dynamical behavior that we attribute to the relaxed anionic form. 

The possibility of reflection of electrons by an evanescent wave formed upon the total internal reflection of femtosecond light pulses from a dielectric-vacuum interface is quite realistic. The duration of the reflected electron pulses may be as long as 100 fs. In the case of electrons reflecting from a curved evanescent wave, one can simultaneously control the duration of the reflected electron pulse and affect its focusing (Fig. lc). Of course, one can imagine many other schemes for controlling the motion of electrons, as is now the case with resonant laser radiation of moderate intensity [9, 10]. In other words, one can think of the possibility of developing femtosecond laser-induced electron optics. Such ultrashort electron pulses may possibly find application in studies into the molecular dynamics of chemical reactions [1,2]. 

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