On the accuracy of the state space restriction approximation for spin dynamics simulations

J Chem Phys. 2011 Aug 28;135(8):084106. doi: 10.1063/1.3624564.


We present an algebraic foundation for the state space restriction approximation in spin dynamics simulations and derive applicability criteria as well as minimal basis set requirements for practically encountered simulation tasks. The results are illustrated with nuclear magnetic resonance (NMR), electron spin resonance (ESR), dynamic nuclear polarization (DNP), and spin chemistry simulations. It is demonstrated that state space restriction yields accurate results in systems where the time scale of spin relaxation processes approximately matches the time scale of the experiment. Rigorous error bounds and basis set requirements are derived.