Monday, January 16, 2017

Dynamic nuclear polarisation via the integrated solid effect I: theory #DNPNMR

Henstra, A. and W.T. Wenckebach, Dynamic nuclear polarisation via the integrated solid effect I: theory. Mol. Phys., 2013. 112(13): p. 1761-1772.

In the hyperpolarisation method known as dynamic nuclear polarisation (DNP), a small amount of unpaired electron spins is added to the sample containing the nuclear spins and the polarisation of these unpaired electron spins is transferred to the nuclear spins by means of a microwave field. Traditional DNP uses weak continuous wave (CW) microwave fields, so perturbation methods can be used to calculate the polarisation transfer. A much faster transfer of the electron spin polarisation is obtained with the integrated solid effect (ISE) which uses strong pulsed microwave fields. As in nuclear orientation via electron spin locking, the polarisation transfer is coherent, similar to the coherence transfer between nuclear spins. This paper presents a theoretical approach to calculate this polarisation transfer. ISE is successfully used for a fast polarisation transfer from short-lived photo-excited triplet states to the surrounding nuclear spins in molecular crystals. These triplet states are strongly aligned in the photo-excitation process and do not require the low temperatures and strong magnetic fields needed to polarise the electron spins in traditional DNP. In the following paper, the theory is applied to the system naphthalene-h8 doped with pentacene-d14 which provides the photo-excited triplet states, and compared with experimental results.