Chemically induced magnetic spin spectroscopy

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. ... 

CIDNP (chemically induced dynamic nuclear polarization) Non-Boltzmann nuclear spin state distribution produced in thermal or photochemical reactions, usually from colligation and diffusion, or disproportionation of radical pairs, and detected by nuclear magnetic resonance spectroscopy by enhanced absorption or emission signals. 

There are a variety of techniques for the determination of the various parameters of the spin-Hamiltonian. Often applied are Electron Paramagnetic or Spin Resonance (EPR, ESR), Electron Nuclear Double Resonance (ENDOR), Electron Electron Double Resonance (ELDOR), Nuclear Magnetic Resonance (NMR), occassionally utilizing effects of Chemically Induced Dynamic Nuclear Polarization (CIDNP), Optical Detection of Magnetic Resonance (ODMR), Atomic Beam Spectroscopy and Optical Spectroscopy. The extraction of the magnetic parameters from the spectra obtained by application of these and related techniques follows procedures which may in detail depend on the technique, the state of the sample (gaseous, liquid, unordered solid, ordered solid) and on spectral resolution. For particulars, the reader is referred to the general references (D). 

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 measuring of radio-frequency-induced transmissions between magnetic energy levels of atomic nuclei. It is a powerful method for elucidating chemical structures, such as by characterizing material by the number, nature, and environment of the hydrogen atoms present in a molecule. This technique is used to solve problems of crystallinity, polymer configuration, and chain structure. See chemistry, analytical electron spin resonance spectroscopy thermal analysis. 

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