Optical nuclear polarization theory

A major limitation for NMR spectroscopy is the intrinsically low sensitivity due to the rather unfavorable Boltzmann distribution for nuclear spins at thermal equilibrium. Thus, considerable effort in magnetic resonance spectroscopy is made towards sensitivity enhancement by hyperpolarization techniques, such as optical polarization, para-hydrogen-induced polarization enhancement, and dynamic nuclear polarization (DNP), a method which exploits the magnetization of unpaired electrons in stable radicals or transition metals to enhance nuclear polarization beyond the Boltzmann limit. In the chapter Dynamic Nuclear Hyperpolarization in Liquids, the fundamental theory for different polarization transfer... 

We present a derivation of the broadening due to the solvent according to a system/ bath quantum approach, originally worked out in the field of solid-state physics to treat the effect of electron/phonon couplings in the electronic transitions of electron traps in crystals [67, 68]. This approach has the advantage to treat all the nuclear degrees of freedom of the system solute/medium on the same foot, namely as coupled oscillators. The same type of approach has been adopted by Jortner and co-workers [69] to derive a quantum theory of thermal electron transfer in polar solvents. In that case, the solvent outside the first solvation shell was treated as a dielectric continuum and, in the frame of the polaron theory, the vibrational modes of the outer medium, that is, the polar modes, play the same role as the lattice optical modes of the crystal investigated elsewhere [67,68]. The total Hamiltonian of the solute (5) and the medium (m) can be formally written as... 

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