Grid-free powder averages: on the applications of the Fokker-Planck equation to solid state NMR.
We demonstrate that Fokker-Planck equations in which spatial coordinates are treated on the same conceptual level as spin coordinates yield a convenient formalism for treating magic angle spinning NMR experiments. In particular, time dependence disappears from the background Hamiltonian (sample spinning is treated as an interaction), spherical quadrature grids are avoided completely (coordinate distributions are a part of the formalism) and relaxation theory with any linear diffusion operator is easily adopted from the Stochastic Liouville Equation theory. The proposed formalism contains Floquet theory as a special case. The elimination of the spherical averaging grid comes at the cost of increased matrix dimensions, but we show that this can be mitigated by the use of state space restriction and tensor train techniques. It is also demonstrated that low correlation order basis sets apparently give accurate answers in powder-averaged MAS simulations, meaning that polynomially scaling simulation algorithms do exist for a large class of solid state NMR experiments.
Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford, South Parks Road, Oxford OX1 3QG, UK; School of Chemistry, University of Southampton, Highfield Campus, Southampton SO17 1BJ, UK.
Luke J
LJ
Edwards
D V
DV
Savostyanov
A A
AA
Nevzorov
M
M
Concistrè
G
G
Pileio
Ilya
I
Kuprov
Fokker–Planck equation; MAS; NMR; SLE; State space restriction